WorldWideScience

Sample records for defect reaction kinetics

  1. Kinetic Monte Carlo studies of the reaction kinetics of crystal defects that diffuse one-dimensionally with occasional transverse migration

    DEFF Research Database (Denmark)

    Heinisch, H.L.; Trinkaus, H.; Singh, Bachu Narain

    2007-01-01

    The reaction kinetics of the various species of mobile defects in irradiated materials are crucially dependent on the dimensionality of their migration. Sink strengths for one-dimensionally (1D) gliding interstitial loops undergoing occasional direction changes have been described analytically...

  2. Reaction kinetics of bond rotations in graphene

    KAUST Repository

    Skowron, Stephen T.; Koroteev, Victor O.; Baldoni, Matteo; Lopatin, Sergei; Zurutuza, Amaia; Chuvilin, Andrey; Besley, Elena

    2016-01-01

    The formation and healing processes of the fundamental topological defect in graphitic materials, the Stone-Wales (SW) defect, are brought into a chemical context by considering the rotation of a carbon-carbon bond as chemical reaction. We investigate the rates and mechanisms of these SW transformations in graphene at the atomic scale using transmission electron microscopy. We develop a statistical atomic kinetics formalism, using direct observations obtained under different conditions to determine key kinetic parameters of the reactions. Based on the obtained statistics we quantify thermally and irradiation induced routes, identifying a thermal process of healing with an activation energy consistent with predicted adatom catalysed mechanisms. We discover exceptionally high rates for irradiation induced SW healing, incompatible with the previously assumed mechanism of direct knock-on damage and indicating the presence of an efficient nonadiabatic coupling healing mechanism involving beam induced electronic excitations of the SW defect.

  3. Reaction kinetics of bond rotations in graphene

    KAUST Repository

    Skowron, Stephen T.

    2016-04-12

    The formation and healing processes of the fundamental topological defect in graphitic materials, the Stone-Wales (SW) defect, are brought into a chemical context by considering the rotation of a carbon-carbon bond as chemical reaction. We investigate the rates and mechanisms of these SW transformations in graphene at the atomic scale using transmission electron microscopy. We develop a statistical atomic kinetics formalism, using direct observations obtained under different conditions to determine key kinetic parameters of the reactions. Based on the obtained statistics we quantify thermally and irradiation induced routes, identifying a thermal process of healing with an activation energy consistent with predicted adatom catalysed mechanisms. We discover exceptionally high rates for irradiation induced SW healing, incompatible with the previously assumed mechanism of direct knock-on damage and indicating the presence of an efficient nonadiabatic coupling healing mechanism involving beam induced electronic excitations of the SW defect.

  4. The effects of one-dimensional glide on the reaction kinetics of interstitial clusters

    DEFF Research Database (Denmark)

    Heinisch, H.L.; Singh, B.N.; Golubov, S.I.

    2000-01-01

    is therefore 'mixed 1D/3D migration' along a 3D path consisting of 1D segments, The defect reaction kinetics under mixed 1D/3D diffusion are different from pure 1D diffusion and pure 3D diffusion, both of which can be formulated within analytical rate theory models of microstructure evolution under irradiation....... Atomic-scale kinetic Monte Carlo (kMC) defect migration simulations are used to investigate the effects of mixed 1D/3D migration on defect reaction kinetics as a guide for implementing mixed 1D/3D migration into the analytical rate theory. The functional dependence of the sink strength on the size...

  5. Reaction kinetic analysis of reactor surveillance data

    Energy Technology Data Exchange (ETDEWEB)

    Yoshiie, T., E-mail: yoshiie@rri.kyoto-u.ac.jp [Research Reactor Institute, Kyoto University, Kumatori-cho, Sennan-gun, Osaka-fu 590-0494 (Japan); Kinomura, A. [Research Reactor Institute, Kyoto University, Kumatori-cho, Sennan-gun, Osaka-fu 590-0494 (Japan); Nagai, Y. [The Oarai Center, Institute for Materials Research, Tohoku University, Oarai, Ibaraki 311-1313 (Japan)

    2017-02-15

    In the reactor pressure vessel surveillance data of a European-type pressurized water reactor (low-Cu steel), it was found that the concentration of matrix defects was very high, and a large number of precipitates existed. In this study, defect structure evolution obtained from surveillance data was simulated by reaction kinetic analysis using 15 rate equations. The saturation of precipitation and the growth of loops were simulated, but it was not possible to explain the increase in DBTT on the basis of the defect structures. The sub-grain boundary segregation of solutes was discussed for the origin of the DBTT increase.

  6. 1D to 3D diffusion-reaction kinetics of defects in crystals

    DEFF Research Database (Denmark)

    Trinkaus, H.; Heinisch, H.L.; Barashev, A.V.

    2002-01-01

    Microstructural features evolving in crystalline solids from diffusion-reaction kinetics of mobile components depend crucially on the dimension of the underlying diffusion process which is commonly assumed to be three-dimensional (3D). In metals, irradiation-induced displacement cascades produce...... clusters of self-interstitials performing 1D diffusion. Changes between equivalent 1D diffusion paths and transversal diffusion result in diffusion-reaction kinetics between one and three dimensions. An analytical approach suggests a single-variable function (master curve) interpolating between the 1D...

  7. The theory of dissipative structures of the kinetic system for defects of nonlinear physical system 'metal+loading+irradiation'. Part 3

    International Nuclear Information System (INIS)

    Tarasov, V.A.; Borikov, T.L.; Kryzhanovskaya, T.V.; Chernezhenko, S.A.; Rusov, V.D.

    2007-01-01

    The kinetic system for defects of physical nonlinear system 'metal + load + irradiation' is specified [1, 2, 3]. Developing the approaches offered in [4], where distinctions of mechanisms of radiating creep and areas of their applicability are formalized (depending on external parameters) for fuel and constructional metals, division of kinetic systems for defects of constructional and fuel metals is carrying out. Thus the accent on the autocatalytic features of kinetic system for defects of reactor fuel metals, resulting from the exoenergic autocatalytic character of nuclear fission reactions being the main point defect source is done. In this part of the article the basic attention is given to the kinetic of sink drains for point defects. For kinetic systems of sinks-sources new approaches for the task of boundary conditions are offered. The possible structure of the computer program modelling kinetic system for defects of nonlinear physical system 'metal + load + irradiation' is considered

  8. Electrical characterization of copper related defect reactions in silicon

    Energy Technology Data Exchange (ETDEWEB)

    Heiser, T. [Centre National de la Recherche Scientifique, 67 - Strasbourg (France). Lab. PHASE; Istratov, A.A.; Flink, C.; Weber, E.R. [Department of Material Science and Mineral Engineering, University of California at Berkeley, 577 Evans Hall, Berkeley, CA 94720 (United States)

    1999-02-12

    Defect reactions involving interstitial copper impurities (Cu{sub i}) in silicon are reviewed. The influence of the Coulomb interaction between positively charged copper and negatively charged defects, such as acceptor states of transition metals and lattice defects, on the complex formation rate is discussed in detail. The diffusivity of interstitial copper and the dissociation kinetics of copper-acceptor pairs are studied using the recently introduced transient ion drift (TID) method. TID results reveal that most interstitial copper impurities remain dissolved immediately after the quench and form pairs with shallow acceptors. It is shown that in moderately and heavily doped silicon the diffusivity of copper is trap limited, while in low B-doped silicon the interstitial copper-acceptor pairing is weak enough to allow the assessment of the copper intrinsic diffusion coefficient. The intrinsic diffusion barrier is estimated to be 0.18{+-}0.01 eV. It is concluded that the Coulomb potential used in previous publications underestimated considerably the acceptor-copper interaction. In light of these results, a general discussion on Cu related defect reactions is given. (orig.) 44 refs.

  9. Chemical kinetics and reaction mechanism

    International Nuclear Information System (INIS)

    Jung, Ou Sik; Park, Youn Yeol

    1996-12-01

    This book is about chemical kinetics and reaction mechanism. It consists of eleven chapters, which deal with reaction and reaction speed on reaction mechanism, simple reaction by rate expression, reversible reaction and simultaneous reaction, successive reaction, complicated reaction mechanism, assumption for reaction mechanism, transition state theory, successive reaction and oscillating reaction, reaction by solution, research method high except kinetics on reaction mechanism, high reaction of kinetics like pulsed radiolysis.

  10. Derivation of kinetic coefficients by atomistic methods for studying defect behavior in Mo

    International Nuclear Information System (INIS)

    Insepov, Z.; Rest, J.; Yacout, A.M.; Kuksin, A.Yu.; Norman, G.E.; Stegailov, V.V.; Starikov, S.V.; Yanilkin, A.V.

    2012-01-01

    Highlights: ► A multiscale concept couples molecular dynamics (MD) with ab initio and kinetic rate theory. ► Evolution of a system of self-interstitial atoms and vacancies in Mo is studied by MD. ► Formation of di-SIA clusters and SIA–vacancy recombination is analyzed. ► 1D diffusion of self-interstitials at various temperature and defect concentrations were studied. ► This paper provides a powerful predictive tool for simulating irradiation of nuclear materials. - Abstract: A multiscale concept for irradiated materials simulation is formulated based on coupling molecular dynamics simulations (MD) where the potential was obtained from ab initio data of energies of the basic defect structures, with kinetic mesoscale models. The evolution of a system containing self-interstitial atoms (SIAs) and vacancies in crystalline molybdenum is investigated by means of MD. The kinetics of formation of di-SIA clusters and SIA–vacancy recombination is analyzed via approaches used in the kinetic theory of radiation ageing. The effects of 1D diffusion of SIAs, temperature, and defect concentrations on the reaction rates are also studied. This approach can validate both the kinetic mechanisms and the appropriate kinetic coefficients, offering the potential to significantly reduce the uncertainty of the kinetic methodology and providing a powerful predictive tool for simulating irradiation behavior of nuclear materials.

  11. Chemical kinetics of gas reactions

    CERN Document Server

    Kondrat'Ev, V N

    2013-01-01

    Chemical Kinetics of Gas Reactions explores the advances in gas kinetics and thermal, photochemical, electrical discharge, and radiation chemical reactions. This book is composed of 10 chapters, and begins with the presentation of general kinetic rules for simple and complex chemical reactions. The next chapters deal with the experimental methods for evaluating chemical reaction mechanisms and some theories of elementary chemical processes. These topics are followed by discussions on certain class of chemical reactions, including unimolecular, bimolecular, and termolecular reactions. The rema

  12. The Effects of One-Dimensional Glide on the Reaction Kinetics of Interstitial Clusters

    International Nuclear Information System (INIS)

    Heinisch, Howard L.; Singh, B N.; Golubov, S I.

    2000-01-01

    Collision cascades in metals produce small interstitial clusters and perfect dislocation loops that glide in thermally activated one-dimensional (1D) random walks. These gliding defects can change their Burgers vectors by thermal activation or by interactions with other defects. Their migration is therefore''mixed 1D/3D migration'' along a 3D path consisting of 1D segments. The defect reaction kinetics under mixed 1D/3D diffusion are different from pure 1D diffusion and pure 3D diffusion, both of which can be formulated within analytical rate theory models of microstructure evolution under irradiation. Atomic-scale kinetic Monte Carlo (kMC) defect migration simulations are used to investigate the effects of mixed 1D/3D migration on defect reaction kinetics as a guide for implementing mixed 1D/3D migration into the analytical rate theory. The functional dependence of the sink strength on the sixe and concentration of sinks under mixed 1D/3D migration is shown to lie between that for pure 1D and pure 3D migration and varies with L, the average distance between direction changes of the gliding defects. It is shown that the sink strength in simulations for spherical sinks of radius R under mixed 1D/3D migration for values of L greater than R can be approximated by an expression that varies directly as R2. For small L, the form of the transition from mixed 1D/3D to pure 3D diffusion as L decreases is demonstrated in the simulations, the results of which can be used in the future development of an analytical expression describing this transition region

  13. Defect accumulation under cascade damage conditions

    DEFF Research Database (Denmark)

    Trinkaus, H.; Singh, B.N.; Woo, C.H.

    1994-01-01

    in terms of this reaction kinetics taking into account cluster production, dissociation, migration and annihilation at extended sinks. Microstructural features which are characteristic of cascade damage and cannot be explained in terms of the conventional single defect reaction kinetics are emphasized......There is now ample evidence from both experimental and computer simulation studies that in displacement cascades not only intense recombination takes place but also efficient clustering of both self-interstitial atoms (SIAs) and vacancies. The size distributions of the two types of defects produced...... reactions kinetics associated with the specific features of cascade damage is described, with emphasis on asymmetries between SIA and vacancy type defects concerning their production, stability, mobility and interactions with other defects. Defect accumulation under cascade damage conditions is discussed...

  14. The influence of dislocation defects on the sintering kinetics of ferrite powders

    International Nuclear Information System (INIS)

    Fadeeva, I.V.; Portnoi, K.V.; Oleinikov, N.N.; Tretyakov, D.Yu.

    1976-01-01

    In the presented paper are given the results of the X-ray investigations of non-equilibrium defects in powders of nickel-zinc ferrites. The block size, the crystal lattice microdistortions and stacking faults of two types were determined by the method of Fourier's analysis of diffraction line profiles. The influence of similar defects on sintering of ferrite powders was shown. The kinetics data on densification processes occurring during sintering of active powders can adequately be described in terms of the equations which describe reactions in the solid phase, where the interaction limit is on the border of the phases with different geomtery of the border. The correlation between the behaviour of compacts and dislocation defects in powders during sintering is established

  15. Kinetics of Bio-Reactions

    DEFF Research Database (Denmark)

    Villadsen, John

    2015-01-01

    his chapter predicts the specific rates of reaction by means of a mathematical expression, the kinetics of the reaction. This expression can be derived through a mechanistic interpretation of an enzymatically catalyzed reaction, but it is essentially of empirical nature for cell reactions. The mo...

  16. Kinetic studies of elementary chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Durant, J.L. Jr. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    This program concerning kinetic studies of elementary chemical reactions is presently focussed on understanding reactions of NH{sub x} species. To reach this goal, the author is pursuing experimental studies of reaction rate coefficients and product branching fractions as well as using electronic structure calculations to calculate transition state properties and reaction rate calculations to relate these properties to predicted kinetic behavior. The synergy existing between the experimental and theoretical studies allow one to gain a deeper insight into more complex elementary reactions.

  17. Chemistry and reaction kinetics of biowaste torrefaction

    NARCIS (Netherlands)

    Stelt, van der M.J.C.

    2011-01-01

    This thesis addresses the question of how the chemistry and reaction kinetics of torrefaction are influenced by reaction conditions and the effects occuring during the reaction. This research question can be specified by questions such as, what controls their kinetics during torrefaction and what

  18. Discussion of the Investigation Method on the Reaction Kinetics of Metallurgical Reaction Engineering

    Science.gov (United States)

    Du, Ruiling; Wu, Keng; Zhang, Jiazhi; Zhao, Yong

    Reaction kinetics of metallurgical physical chemistry which was successfully applied in metallurgy (as ferrous metallurgy, non-ferrous metallurgy) became an important theoretical foundation for subject system of traditional metallurgy. Not only the research methods were very perfect, but also the independent structures and systems of it had been formed. One of the important tasks of metallurgical reaction engineering was the simulation of metallurgical process. And then, the mechanism of reaction process and the conversion time points of different control links should be obtained accurately. Therefore, the research methods and results of reaction kinetics in metallurgical physical chemistry were not very suitable for metallurgical reaction engineering. In order to provide the definite conditions of transmission, reaction kinetics parameters and the conversion time points of different control links for solving the transmission and reaction equations in metallurgical reaction engineering, a new method for researching kinetics mechanisms in metallurgical reaction engineering was proposed, which was named stepwise attempt method. Then the comparison of results between the two methods and the further development of stepwise attempt method were discussed in this paper. As a new research method for reaction kinetics in metallurgical reaction engineering, stepwise attempt method could not only satisfy the development of metallurgical reaction engineering, but also provide necessary guarantees for establishing its independent subject system.

  19. Hydrogen electrode reaction: A complete kinetic description

    International Nuclear Information System (INIS)

    Quaino, P.M.; Gennero de Chialvo, M.R.; Chialvo, A.C.

    2007-01-01

    The kinetic description of the hydrogen electrode reaction (HER) in the whole range of overpotentials (-0.2 < η (V) < 0.40) is presented. The Volmer-Heyrovsky-Tafel mechanism was solved considering simultaneously the following items: (i) the diffusional contribution of the molecular hydrogen from and towards the electrode surface, (ii) the forward and backward reaction rates of each elementary step and (iii) a Frumkin type adsorption for the reaction intermediate. In order to verify the descriptive capability of the kinetic expressions derived, an experimental study of the HER was carried out on a rotating platinum disc electrode in acid solution. From the correlation of these results the elementary kinetic parameters were evaluated and several aspects related to the kinetic mechanism were discussed. Finally, the use of these kinetic expressions to interpret results obtained on microelectrodes is also analysed

  20. Defect and dopant kinetics in laser anneals of Si

    International Nuclear Information System (INIS)

    La Magna, A.; Fisicaro, G.; Mannino, G.; Privitera, V.; Piccitto, G.; Svensson, B.G.; Vines, L.

    2008-01-01

    In this work a modeling approach is applied to investigate the kinetics of the defect-dopant system in the extremely far-from-the equilibrium conditions caused by the laser irradiation in Si. A rigorous derivation of the master equations for the evolution of the defect-impurity system is obtained starting from the Boltzmann's formalism. The model derived is not limited by the stringent hypothesis of instantaneous equilibration of the local system energy to the lattice thermal field. This fact allows: (a) the formalization of a reliable theoretical formalism for the study of evolving defect-impurity systems in a non-uniform fast varying thermal field and (b) the generalization of the kinetic parameters (e.g. diffusivity, clustering rate constants, etc.). Early comparisons between simulations and experimental analysis of the processes are discussed. These results indicate the reliability of the energetic calibration for the self-interstitial clusters derived using conventional thermal processes

  1. Preventing Corrosion by Controlling Cathodic Reaction Kinetics

    Science.gov (United States)

    2016-03-25

    3. DATES COVERED (From - To) 09/23/15 - 04/22/16 4. TITLE AND SUBTITLE Sa. CONTRACT NUMBER Preventing Corrosion by Controlling Cathodic Reaction...Preventing corrosion by controlling cathodic reaction kinetics Progress Report for Period: 1 SEP 2015-31 MAR 2016 John Keith Department of...25 March 2016 Preventing corrosion by controlling cathodic reaction kinetics Annual Summary Report: FY16 PI: John Keith, 412-624-7016,jakeith

  2. Behaviour of defective CANDU fuel: fuel oxidation kinetic and thermodynamic modelling

    International Nuclear Information System (INIS)

    Higgs, J.

    2005-01-01

    The thermal performance of operating CANDU fuel under defect conditions is affected by the ingress of heavy water into the fuel element. A mechanistic model has been developed to predict the extent of fuel oxidation in defective fuel and its affect on fuel thermal performance. A thermodynamic treatment of such oxidized fuel has been performed as a basis for the boundary conditions in the kinetic model. Both the kinetic and thermodynamic models have been benchmarked against recent experimental work. (author)

  3. Combustion kinetics and reaction pathways

    Energy Technology Data Exchange (ETDEWEB)

    Klemm, R.B.; Sutherland, J.W. [Brookhaven National Laboratory, Upton, NY (United States)

    1993-12-01

    This project is focused on the fundamental chemistry of combustion. The overall objectives are to determine rate constants for elementary reactions and to elucidate the pathways of multichannel reactions. A multitechnique approach that features three independent experiments provides unique capabilities in performing reliable kinetic measurements over an exceptionally wide range in temperature, 300 to 2500 K. Recent kinetic work has focused on experimental studies and theoretical calculations of the methane dissociation system (CH{sub 4} + Ar {yields} CH{sub 3} + H + Ar and H + CH{sub 4} {yields} CH{sub 3} + H{sub 2}). Additionally, a discharge flow-photoionization mass spectrometer (DF-PIMS) experiment is used to determine branching fractions for multichannel reactions and to measure ionization thresholds of free radicals. Thus, these photoionization experiments generate data that are relevant to both reaction pathways studies (reaction dynamics) and fundamental thermochemical research. Two distinct advantages of performing PIMS with high intensity, tunable vacuum ultraviolet light at the National Synchrotron Light Source are high detection sensitivity and exceptional selectivity in monitoring radical species.

  4. Reaction kinetics of polybutylene terephthalate polycondensation reaction

    NARCIS (Netherlands)

    Darda, P. J.; Hogendoorn, J. A.; Versteeg, G. F.; Souren, F.

    2005-01-01

    The kinetics of the forward polycondensation reaction of polybutylene terephthalate (PBT) has been investigated using thermogravimetric analysis (TGA). PBT - prepolymer with an initial degree of polymerization of 5.5 was used as starting material. The PBT prepolymer was prepared from dimethyl

  5. Kinetic aspects of the Maillard reaction: a critical review

    NARCIS (Netherlands)

    Boekel, van M.A.J.S.

    2001-01-01

    The literature concerning the kinetics of the Maillard reaction was critically discussed according to the initial, intermediate and advanced stages, as this is the way the Maillard reaction is traditionally analysed. For each stage, a division is made between simple kinetics and complex kinetics.

  6. A Kinetic Study of the Diels-Alder Reaction. An Experiment Illustrating Simple Second-Order Reaction Kinetics.

    Science.gov (United States)

    Silvestri, Michael G.; Dills, Charles E.

    1989-01-01

    Describes an organic chemistry experiment for teaching the basic concepts of chemical kinetics. Provides background information about first- and second-order reactions, experimental procedures of the Diels-Alder reaction between cyclopentadiene and dimethyl fumarate, and the experimental results. (YP)

  7. Enzyme-catalyzed and binding reaction kinetics determined by titration calorimetry.

    Science.gov (United States)

    Hansen, Lee D; Transtrum, Mark K; Quinn, Colette; Demarse, Neil

    2016-05-01

    Isothermal calorimetry allows monitoring of reaction rates via direct measurement of the rate of heat produced by the reaction. Calorimetry is one of very few techniques that can be used to measure rates without taking a derivative of the primary data. Because heat is a universal indicator of chemical reactions, calorimetry can be used to measure kinetics in opaque solutions, suspensions, and multiple phase systems and does not require chemical labeling. The only significant limitation of calorimetry for kinetic measurements is that the time constant of the reaction must be greater than the time constant of the calorimeter which can range from a few seconds to a few minutes. Calorimetry has the unique ability to provide both kinetic and thermodynamic data. This article describes the calorimetric methodology for determining reaction kinetics and reviews examples from recent literature that demonstrate applications of titration calorimetry to determine kinetics of enzyme-catalyzed and ligand binding reactions. A complete model for the temperature dependence of enzyme activity is presented. A previous method commonly used for blank corrections in determinations of equilibrium constants and enthalpy changes for binding reactions is shown to be subject to significant systematic error. Methods for determination of the kinetics of enzyme-catalyzed reactions and for simultaneous determination of thermodynamics and kinetics of ligand binding reactions are reviewed. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. Effects of reaction-kinetic parameters on modeling reaction pathways in GaN MOVPE growth

    Science.gov (United States)

    Zhang, Hong; Zuo, Ran; Zhang, Guoyi

    2017-11-01

    In the modeling of the reaction-transport process in GaN MOVPE growth, the selections of kinetic parameters (activation energy Ea and pre-exponential factor A) for gas reactions are quite uncertain, which cause uncertainties in both gas reaction path and growth rate. In this study, numerical modeling of the reaction-transport process for GaN MOVPE growth in a vertical rotating disk reactor is conducted with varying kinetic parameters for main reaction paths. By comparisons of the molar concentrations of major Ga-containing species and the growth rates, the effects of kinetic parameters on gas reaction paths are determined. The results show that, depending on the values of the kinetic parameters, the gas reaction path may be dominated either by adduct/amide formation path, or by TMG pyrolysis path, or by both. Although the reaction path varies with different kinetic parameters, the predicted growth rates change only slightly because the total transport rate of Ga-containing species to the substrate changes slightly with reaction paths. This explains why previous authors using different chemical models predicted growth rates close to the experiment values. By varying the pre-exponential factor for the amide trimerization, it is found that the more trimers are formed, the lower the growth rates are than the experimental value, which indicates that trimers are poor growth precursors, because of thermal diffusion effect caused by high temperature gradient. The effective order for the contribution of major species to growth rate is found as: pyrolysis species > amides > trimers. The study also shows that radical reactions have little effect on gas reaction path because of the generation and depletion of H radicals in the chain reactions when NH2 is considered as the end species.

  9. Role of point defects and additives in kinetics of hydrogen storage materials

    Science.gov (United States)

    van de Walle, Chris

    2010-03-01

    First-principles computational studies of hydrogen interactions with storage materials can provide direct insight into the processes of H uptake and release, and may help in developing guidelines for designing storage media with improved storage capacity and kinetics. One important conclusion is that the defects involved in kinetics of semiconducting or insulating H-storage materials are charged, and hence their formation energy is Fermi-level dependent and can be affected by the presence of impurities that change the Fermi level [1,2]. This provides an explanation for the role played by transition-metal impurities in the kinetics of NaAlH4 and related materials. Desorption of H and decomposition of NaAlH4 requires not only mass transport of H but also of Al and/or Na. This process is mediated by native defects. We have investigated the structure, stability, and migration enthalpy of native defects based on density functional theory. The results allow us to estimate diffusion activation energies for the defects that may be involved in mass transport. Most of the relevant defects exist in charge states other than neutral, and consideration of these charge states is essential for a proper description of kinetics. We propose specific new mechanisms to explain the observed activation energies and their dependence on the presence of impurities. We have also expanded our studies to materials other than NaAlH4. In the case of LiBH4 and Li4BN3H10 we have found that the calculations have predictive power in terms of identifying which impurities will actually enhance kinetics. Other complex hydrides that we are currently investigating include Li2NH and LiNH2. [4pt] [1] A. Peles and C. G. Van de Walle, Phys. Rev. B 76, 214101 (2007). [0pt] [2] C. G. Van de Walle, A. Peles, A. Janotti, and G. B. Wilson-Short, Physica B 404, 793 (2009).

  10. Ab-initio modelling of thermodynamics and kinetics of point defects in indium oxide

    International Nuclear Information System (INIS)

    Agoston, Peter; Klein, Andreas; Albe, Karsten; Erhart, Paul

    2008-01-01

    The electrical and optical properties of indium oxide films strongly vary with the processing parameters. Especially the oxygen partial pressure and temperature determine properties like electrical conductivity, composition and transparency. Since this material owes its remarkable properties like the intrinsic n-type conductivity to its defect chemistry, it is important to understand both, the equilibrium defect thermodynamics and kinetics of the intrinsic point defects. In this contribution we present a defect model based on DFT total energy calculations using the GGA+U method. Further, the nudged elastic band method is employed in order to obtain a set of migration barriers for each defect species. Due to the complicated crystal structure of indium oxide a Kinetic Monte-Carlo algorithm was implemented, which allows to determine diffusion coefficients. The bulk tracer diffusion constant is predicted as a function of oxygen partial pressure, Fermi level and temperature for the pure material

  11. Defect kinetics and resistance to amorphization in zirconium carbide

    International Nuclear Information System (INIS)

    Zheng, Ming-Jie; Szlufarska, Izabela; Morgan, Dane

    2015-01-01

    To better understand the radiation response of zirconium carbide (ZrC), and in particular its excellent resistance to amorphization, we have used density functional theory methods to study the kinetics of point defects in ZrC. The migration barriers and recombination barriers of the simple point defects are calculated using the ab initio molecular dynamics simulation and the nudged elastic band method. These barriers are used to estimate C and Zr interstitial and vacancy diffusion and Frenkel pair recombination rates. A significant barrier for C Frenkel pair recombination is found but it is shown that a large concentration of C vacancies reduces this barrier dramatically, allowing facile healing of radiation damage. The mechanisms underlying high resistance to amorphization of ZrC were analyzed from the perspectives of structural, thermodynamic, chemical and kinetic properties. This study provides insights into the amorphization resistance of ZrC as well as a foundation for understanding general radiation damage in this material

  12. Kinetics of gaseous uranium hexafluoride reaction with hydrogen chloride

    International Nuclear Information System (INIS)

    Ezubchenko, A.N.; Ilyukhin, A.I.; Merzlyakov, A.V.

    1993-01-01

    Kinetics of decrease of concentration of gaseous uranium hexafluoride in reaction with hydrogen chloride at temperatures close to room ones, was investigated by the method of IR spectroscopy. It was established that the process represented the first order reaction by both UF 6 and HCl. Activation energy of the reaction was determined: 7.6 ± 0.7 kcal/mol. Specific feature of reaction kinetics was noted: inversely proportional dependence of effective constant on UF 6 initial pressure. 5 refs., 3 figs

  13. Kinetic concepts of thermally stimulated reactions in solids

    Science.gov (United States)

    Vyazovkin, Sergey

    Historical analysis suggests that the basic kinetic concepts of reactions in solids were inherited from homogeneous kinetics. These concepts rest upon the assumption of a single-step reaction that disagrees with the multiple-step nature of solid-state processes. The inadequate concepts inspire such unjustified anticipations of kinetic analysis as evaluating constant activation energy and/or deriving a single-step reaction mechanism for the overall process. A more adequate concept is that of the effective activation energy, which may vary with temperature and extent of conversion. The adequacy of this concept is illustrated by literature data as well as by experimental data on the thermal dehydration of calcium oxalate monohydrate and thermal decomposition of calcium carbonate, ammonium nitrate and 1,3,5,7- tetranitro-1,3,5,7-tetrazocine.

  14. Kinetics of chemical reactions initiated by hot atoms

    International Nuclear Information System (INIS)

    Firsova, L.P.

    1977-01-01

    Modern ideas about kinetics of chemical reactions of hot atoms are generalized. The main points of the phenomenological theories (''kinetic theory'' of Wolfgang-Estrup hot reactions and the theory of ''reactions integral probability'' of Porter) are given. Physico-chemical models of elastic and non-elastic collisions are considered which are used in solving Boltzmann integro-differential equations and stochastic equations in the Porter theory. The principal formulas are given describing probabilities or yields of chemical reactions, initiated with hot atoms, depending on the distribution functions of hot particles with respect to energy. Briefly described are the techniques and the results of applying the phenomenological theories for interpretation of the experimental data obtained during nuclear reactions with hot atoms, photochemical investigations, etc. 96 references are given

  15. Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

    Science.gov (United States)

    Fedorenko, S. G.; Burshtein, A. I.

    2014-09-01

    Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics.

  16. Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

    Energy Technology Data Exchange (ETDEWEB)

    Fedorenko, S. G. [Voevodsky Institute of Chemical Kinetics and Combustion, Novosibirsk (Russian Federation); Burshtein, A. I. [Weizmann Institute of Science, 76100, Rehovot (Israel)

    2014-09-21

    Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics.

  17. Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

    International Nuclear Information System (INIS)

    Fedorenko, S. G.; Burshtein, A. I.

    2014-01-01

    Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics

  18. Kinetic modelling of the Maillard reaction between proteins and sugars

    NARCIS (Netherlands)

    Brands, C.M.J.

    2002-01-01

    Keywords: Maillard reaction, sugar isomerisation, kinetics, multiresponse modelling, brown colour formation, lysine damage, mutagenicity, casein, monosaccharides, disaccharides, aldoses, ketoses

    The aim of this thesis was to determine the kinetics of the Maillard reaction between

  19. Spectroscopy and reaction kinetics of HCO

    International Nuclear Information System (INIS)

    Guo, Yili.

    1989-01-01

    The high-resolution infrared spectrum of the C-H stretching fundamental of HCO has been studied by means of infrared flash kinetic spectroscopy. HCO was generated by flash photolysis of acetaldehyde or formaldehyde using a 308 nm (XeCl) excimer laser. The transient absorption was probed with an infrared difference frequency laser system. The high resolution spectra obtained were assigned and fitted with rotational, spin-rotational, and centrifugal distortion constants. The ν 1 band origin is 2434.48 cm/sup /minus/1/. New ground state constants have been derived from a least-squares fit combining the ν 1 data with previous microwave and FIR LMR measurements. A new set of spectroscopic constants for the (1, 0, 0) state, the equilibrium rotational constants, and the orientation of the transition dipole moment are also reported. The kinetics and product branching ratios of the HCO + NO 2 reaction have been studied using visible and infrared laser flash kinetic spectroscopy. The rate constant for the disappearance of HCO radical at 296 K is (5.7 +- 0.9) /times/ 10/sup /minus/11/ cm 3 molec/sup /minus/1/ sec/sup /minus/1/, and it is independent of the pressure of SF 6 buffer gas up to 700 torr. Less than 10% of the reaction goes through the most exothermic product channel, HNO + CO 2 . The product channel, H + CO 2 + NO, is responsible for 52% of the reaction. HONO has been observed, though not quantitatively, as a reaction product corresponding to the HONO + CO channel. 51 refs., 21 figs., 8 tabs

  20. Kinetics of phase transformations

    International Nuclear Information System (INIS)

    Thompson, M.O.; Aziz, M.J.; Stephenson, G.B.

    1992-01-01

    This volume contains papers presented at the Materials Research Society symposium on Kinetics of Phase Transformations held in Boston, Massachusetts from November 26-29, 1990. The symposium provided a forum for research results in an exceptionally broad and interdisciplinary field. Presentations covered nearly every major class of transformations including solid-solid, liquid-solid, transport phenomena and kinetics modeling. Papers involving amorphous Si, a dominant topic at the symposium, are collected in the first section followed by sections on four major areas of transformation kinetics. The symposium opened with joint sessions on ion and electron beam induced transformations in conjunction with the Surface Chemistry and Beam-Solid Interactions: symposium. Subsequent sessions focused on the areas of ordering and nonlinear diffusion kinetics, solid state reactions and amorphization, kinetics and defects of amorphous silicon, and kinetics of melting and solidification. Seven internationally recognized invited speakers reviewed many of the important problems and recent results in these areas, including defects in amorphous Si, crystal to glass transformations, ordering kinetics, solid-state amorphization, computer modeling, and liquid/solid transformations

  1. SABIO-RK: A data warehouse for biochemical reactions and their kinetics

    Directory of Open Access Journals (Sweden)

    Krebs Olga

    2007-03-01

    Full Text Available Systems biology is an emerging field that aims at obtaining a system-level understanding of biological processes. The modelling and simulation of networks of biochemical reactions have great and promising application potential but require reliable kinetic data. In order to support the systems biology community with such data we have developed SABIO-RK (System for the Analysis of Biochemical Pathways - Reaction Kinetics, a curated database with information about biochemical reactions and their kinetic properties, which allows researchers to obtain and compare kinetic data and to integrate them into models of biochemical networks. SABIO-RK is freely available for academic use at http://sabio.villa-bosch.de/SABIORK/.

  2. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

    International Nuclear Information System (INIS)

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C.; Brooks, Scott C; Pace, Molly; Kim, Young Jin; Jardine, Philip M.; Watson, David B.

    2007-01-01

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M. partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M. species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing NE equilibrium reactions and a set of reactive transport equations of M-NE kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions

  3. A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions.

    Science.gov (United States)

    Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C; Brooks, Scott C; Pace, Molly N; Kim, Young-Jin; Jardine, Philip M; Watson, David B

    2007-06-16

    This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing N(E) equilibrium reactions and a set of reactive transport equations of M-N(E) kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

  4. Understanding Chemical Reaction Kinetics and Equilibrium with Interlocking Building Blocks

    Science.gov (United States)

    Cloonan, Carrie A.; Nichol, Carolyn A.; Hutchinson, John S.

    2011-01-01

    Chemical reaction kinetics and equilibrium are essential core concepts of chemistry but are challenging topics for many students, both at the high school and undergraduate university level. Visualization at the molecular level is valuable to aid understanding of reaction kinetics and equilibrium. This activity provides a discovery-based method to…

  5. Analysis of kinetic reaction mechanisms

    CERN Document Server

    Turányi, Tamás

    2014-01-01

    Chemical processes in many fields of science and technology, including combustion, atmospheric chemistry, environmental modelling, process engineering, and systems biology, can be described by detailed reaction mechanisms consisting of numerous reaction steps. This book describes methods for the analysis of reaction mechanisms that are applicable in all these fields. Topics addressed include: how sensitivity and uncertainty analyses allow the calculation of the overall uncertainty of simulation results and the identification of the most important input parameters, the ways in which mechanisms can be reduced without losing important kinetic and dynamic detail, and the application of reduced models for more accurate engineering optimizations. This monograph is invaluable for researchers and engineers dealing with detailed reaction mechanisms, but is also useful for graduate students of related courses in chemistry, mechanical engineering, energy and environmental science and biology.

  6. Kinetic study of UV-irradiated amorphous sulfur by EPR spectroscopy

    International Nuclear Information System (INIS)

    El Mkami, H.; Smith, G.M.

    2005-01-01

    Electron paramagnetic resonance (EPR) spectroscopy is used to investigate UV-irradiation damage in amorphous sulfur by examining post-irradiation kinetics as a function of UV-exposure time. The kinetic study is described by first-order concurrent reactions where the sulfur, as reactant, undergoes two parallel processes leading to the formation of two distinct defects called S 1 * and S 2 *. The temperature dependence of the EPR intensities of the signals, related to these defects, is used in the kinetic study

  7. First-principles thermodynamics and defect kinetics guidelines for engineering a tailored RRAM device

    International Nuclear Information System (INIS)

    Clima, Sergiu; Chen, Yang Yin; Goux, Ludovic; Govoreanu, Bogdan; Degraeve, Robin; Fantini, Andrea; Jurczak, Malgorzata; Chen, Chao Yang; Pourtois, Geoffrey

    2016-01-01

    Resistive Random Access Memories are among the most promising candidates for the next generation of non-volatile memory. Transition metal oxides such as HfOx and TaOx attracted a lot of attention due to their CMOS compatibility. Furthermore, these materials do not require the inclusion of extrinsic conducting defects since their operation is based on intrinsic ones (oxygen vacancies). Using Density Functional Theory, we evaluated the thermodynamics of the defects formation and the kinetics of diffusion of the conducting species active in transition metal oxide RRAM materials. The gained insights based on the thermodynamics in the Top Electrode, Insulating Matrix and Bottom Electrode and at the interfaces are used to design a proper defect reservoir, which is needed for a low-energy reliable switching device. The defect reservoir has also a direct impact on the retention of the Low Resistance State due to the resulting thermodynamic driving forces. The kinetics of the diffusing conducting defects in the Insulating Matrix determine the switching dynamics and resistance retention. The interface at the Bottom Electrode has a significant impact on the low-current operation and long endurance of the memory cell. Our first-principles findings are confirmed by experimental measurements on fabricated RRAM devices.

  8. First-principles thermodynamics and defect kinetics guidelines for engineering a tailored RRAM device

    Energy Technology Data Exchange (ETDEWEB)

    Clima, Sergiu, E-mail: clima@imec.be; Chen, Yang Yin; Goux, Ludovic; Govoreanu, Bogdan; Degraeve, Robin; Fantini, Andrea; Jurczak, Malgorzata [imec, Kapeldreef 75, 3001 Leuven (Belgium); Chen, Chao Yang [imec, Kapeldreef 75, 3001 Leuven (Belgium); Katholieke Universiteit Leuven, 3001 Leuven (Belgium); Pourtois, Geoffrey [imec, Kapeldreef 75, 3001 Leuven (Belgium); PLASMANT, University of Antwerp, 2610 Antwerpen (Belgium)

    2016-06-14

    Resistive Random Access Memories are among the most promising candidates for the next generation of non-volatile memory. Transition metal oxides such as HfOx and TaOx attracted a lot of attention due to their CMOS compatibility. Furthermore, these materials do not require the inclusion of extrinsic conducting defects since their operation is based on intrinsic ones (oxygen vacancies). Using Density Functional Theory, we evaluated the thermodynamics of the defects formation and the kinetics of diffusion of the conducting species active in transition metal oxide RRAM materials. The gained insights based on the thermodynamics in the Top Electrode, Insulating Matrix and Bottom Electrode and at the interfaces are used to design a proper defect reservoir, which is needed for a low-energy reliable switching device. The defect reservoir has also a direct impact on the retention of the Low Resistance State due to the resulting thermodynamic driving forces. The kinetics of the diffusing conducting defects in the Insulating Matrix determine the switching dynamics and resistance retention. The interface at the Bottom Electrode has a significant impact on the low-current operation and long endurance of the memory cell. Our first-principles findings are confirmed by experimental measurements on fabricated RRAM devices.

  9. Rate kernel theory for pseudo-first-order kinetics of diffusion-influenced reactions and application to fluorescence quenching kinetics.

    Science.gov (United States)

    Yang, Mino

    2007-06-07

    Theoretical foundation of rate kernel equation approaches for diffusion-influenced chemical reactions is presented and applied to explain the kinetics of fluorescence quenching reactions. A many-body master equation is constructed by introducing stochastic terms, which characterize the rates of chemical reactions, into the many-body Smoluchowski equation. A Langevin-type of memory equation for the density fields of reactants evolving under the influence of time-independent perturbation is derived. This equation should be useful in predicting the time evolution of reactant concentrations approaching the steady state attained by the perturbation as well as the steady-state concentrations. The dynamics of fluctuation occurring in equilibrium state can be predicted by the memory equation by turning the perturbation off and consequently may be useful in obtaining the linear response to a time-dependent perturbation. It is found that unimolecular decay processes including the time-independent perturbation can be incorporated into bimolecular reaction kinetics as a Laplace transform variable. As a result, a theory for bimolecular reactions along with the unimolecular process turned off is sufficient to predict overall reaction kinetics including the effects of unimolecular reactions and perturbation. As the present formulation is applied to steady-state kinetics of fluorescence quenching reactions, the exact relation between fluorophore concentrations and the intensity of excitation light is derived.

  10. Formation kinetics of gemfibrozil chlorination reaction products: analysis and application.

    Science.gov (United States)

    Krkosek, Wendy H; Peldszus, Sigrid; Huck, Peter M; Gagnon, Graham A

    2014-07-01

    Aqueous chlorination kinetics of the lipid regulator gemfibrozil and the formation of reaction products were investigated in deionized water over the pH range 3 to 9, and in two wastewater matrices. Chlorine oxidation of gemfibrozil was found to be highly dependent on pH. No statistically significant degradation of gemfibrozil was observed at pH values greater than 7. Gemfibrozil oxidation between pH 4 and 7 was best represented by first order kinetics. At pH 3, formation of three reaction products was observed. 4'-C1Gem was the only reaction product formed from pH 4-7 and was modeled with zero order kinetics. Chlorine oxidation of gemfibrozil in two wastewater matrices followed second order kinetics. 4'-C1Gem was only formed in wastewater with pH below 7. Deionized water rate kinetic models were applied to two wastewater effluents with gemfibrozil concentrations reported in literature in order to calculate potential mass loading rates of 4'C1Gem to the receiving water.

  11. Kinetics of subdiffusion-assisted reactions: non-Markovian stochastic Liouville equation approach

    International Nuclear Information System (INIS)

    Shushin, A I

    2005-01-01

    Anomalous specific features of the kinetics of subdiffusion-assisted bimolecular reactions (time-dependence, dependence on parameters of systems, etc) are analysed in detail with the use of the non-Markovian stochastic Liouville equation (SLE), which has been recently derived within the continuous-time random-walk (CTRW) approach. In the CTRW approach, subdiffusive motion of particles is modelled by jumps whose onset probability distribution function is of a long-tailed form. The non-Markovian SLE allows for rigorous describing of some peculiarities of these reactions; for example, very slow long-time behaviour of the kinetics, non-analytical dependence of the reaction rate on the reactivity of particles, strong manifestation of fluctuation kinetics showing itself in very slowly decreasing behaviour of the kinetics at very long times, etc

  12. Kinetic modeling of reactions in Foods

    NARCIS (Netherlands)

    Boekel, van M.A.J.S.

    2008-01-01

    The level of quality that food maintains as it travels down the production-to-consumption path is largely determined by the chemical, biochemical, physical, and microbiological changes that take place during its processing and storage. Kinetic Modeling of Reactions in Foods demonstrates how to

  13. Synergistic Interlayer and Defect Engineering in VS2 Nanosheets toward Efficient Electrocatalytic Hydrogen Evolution Reaction

    KAUST Repository

    Zhang, Junjun

    2017-12-27

    A simple one-pot solvothermal method is reported to synthesize VS2 nanosheets featuring rich defects and an expanded (001) interlayer spacing as large as 1.00 nm, which is a ≈74% expansion as relative to that (0.575 nm) of the pristine counterpart. The interlayer-expanded VS2 nanosheets show extraordinary kinetic metrics for electrocatalytic hydrogen evolution reaction (HER), exhibiting a low overpotential of 43 mV at a geometric current density of 10 mA cm-2 , a small Tafel slope of 36 mV dec-1 , and long-term stability of 60 h without any current fading. The performance is much better than that of the pristine VS2 with a normal interlayer spacing, and even comparable to that of the commercial Pt/C electrocatalyst. The outstanding electrocatalytic activity is attributed to the expanded interlayer distance and the generated rich defects. Increased numbers of exposed active sites and modified electronic structures are achieved, resulting in an optimal free energy of hydrogen adsorption (∆GH ) from density functional theory calculations. This work opens up a new door for developing transition-metal dichalcogenide nanosheets as high active HER electrocatalysts by interlayer and defect engineering.

  14. Synergistic Interlayer and Defect Engineering in VS2 Nanosheets toward Efficient Electrocatalytic Hydrogen Evolution Reaction

    KAUST Repository

    Zhang, Junjun; Zhang, Chenhui; Wang, Zhenyu; Zhu, Jian; Wen, Zhiwei; Zhao, Xingzhong; Zhang, Xixiang; Xu, Jun; Lu, Zhouguang

    2017-01-01

    A simple one-pot solvothermal method is reported to synthesize VS2 nanosheets featuring rich defects and an expanded (001) interlayer spacing as large as 1.00 nm, which is a ≈74% expansion as relative to that (0.575 nm) of the pristine counterpart. The interlayer-expanded VS2 nanosheets show extraordinary kinetic metrics for electrocatalytic hydrogen evolution reaction (HER), exhibiting a low overpotential of 43 mV at a geometric current density of 10 mA cm-2 , a small Tafel slope of 36 mV dec-1 , and long-term stability of 60 h without any current fading. The performance is much better than that of the pristine VS2 with a normal interlayer spacing, and even comparable to that of the commercial Pt/C electrocatalyst. The outstanding electrocatalytic activity is attributed to the expanded interlayer distance and the generated rich defects. Increased numbers of exposed active sites and modified electronic structures are achieved, resulting in an optimal free energy of hydrogen adsorption (∆GH ) from density functional theory calculations. This work opens up a new door for developing transition-metal dichalcogenide nanosheets as high active HER electrocatalysts by interlayer and defect engineering.

  15. Ametryn degradation by aqueous chlorine: Kinetics and reaction influences

    International Nuclear Information System (INIS)

    Xu Bin; Gao Naiyun; Cheng Hefa; Hu Chenyan; Xia Shengji; Sun Xiaofeng; Wang Xuejiao; Yang Shaogui

    2009-01-01

    The chemical oxidation of the herbicide ametryn was investigated by aqueous chlorination between pH 4 and 10 at a temperature of 25 deg. C. Ametryn was found to react very rapidly with aqueous chlorine. The reaction kinetics can be well described by a second-order kinetic model. The apparent second-order rate constants are greater than 5 x 10 2 M -1 s -1 under acidic and neutral conditions. The reaction proceeds much more slowly under alkaline conditions. The predominant reactions were found to be the reactions of HOCl with neutral ametryn and the charged ametryn, with rate constants equal to 7.22 x 10 2 and 1.58 x 10 3 M -1 s -1 , respectively. The ametryn degradation rate increases with addition of bromide and decreases with addition of ammonia during the chlorination process. Based on elementary chemical reactions, a kinetic model of ametryn degradation by chlorination in the presence of bromide or ammonia ion was also developed. By employing this model, we estimate that the rate constants for the reactions of HOBr with neutral ametryn and charged ametryn were 9.07 x 10 3 and 3.54 x 10 6 M -1 s -1 , respectively. These values are 10- to 10 3 -fold higher than those of HOCl, suggesting that the presence of bromine species during chlorination could significantly accelerate ametryn degradation.

  16. Kinetics of cluster-related defects in silicon sensors irradiated with monoenergetic electrons

    Science.gov (United States)

    Radu, R.; Pintilie, I.; Makarenko, L. F.; Fretwurst, E.; Lindstroem, G.

    2018-04-01

    This work focuses on the kinetic mechanisms responsible for the annealing behavior of radiation cluster-related defects with impact on the electrical performance of silicon sensors. Such sensors were manufactured on high resistivity n-type standard float-zone (STFZ) and oxygen enriched float-zone (DOFZ) material and had been irradiated with mono-energetic electrons of 3.5 MeV energy and fluences of 3 × 1014 cm-2 and 6 × 1014 cm-2. After irradiation, the samples were subjected either to isochronal or isothermal heat treatments in the temperature range from 80 °C to 300 °C. The specific investigated defects are a group of three deep acceptors [H(116 K), H(140 K), and H(152 K)] with energy levels in the lower half of the band gap and a shallow donor E(30 K) with a level at 0.1 eV below the conduction band. The stability and kinetics of these defects at high temperatures are discussed on the basis of the extracted activation energies and frequency factors. The annealing of the H defects takes place similarly in both types of materials, suggesting a migration rather than a dissociation mechanism. On the contrary, the E(30 K) defect shows a very different annealing behavior, being stable in STFZ even at 300 °C, but annealing-out quickly in DOFZ material at temperatures higher than 200 °C , with a high frequency factor of the order of 1013 s-1. Such a behavior rules out a dissociation process, and the different annealing behavior is suggested to be related to a bistable behavior of the defect.

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

    International Nuclear Information System (INIS)

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

    2015-01-01

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

  18. Internal Diffusion-Controlled Enzyme Reaction: The Acetylcholinesterase Kinetics.

    Science.gov (United States)

    Lee, Sangyun; Kim, Ji-Hyun; Lee, Sangyoub

    2012-02-14

    Acetylcholinesterase is an enzyme with a very high turnover rate; it quenches the neurotransmitter, acetylcholine, at the synapse. We have investigated the kinetics of the enzyme reaction by calculating the diffusion rate of the substrate molecule along an active site channel inside the enzyme from atomic-level molecular dynamics simulations. In contrast to the previous works, we have found that the internal substrate diffusion is the determinant of the acetylcholinesterase kinetics in the low substrate concentration limit. Our estimate of the overall bimolecular reaction rate constant for the enzyme is in good agreement with the experimental data. In addition, the present calculation provides a reasonable explanation for the effects of the ionic strength of solution and the mutation of surface residues of the enzyme. The study suggests that internal diffusion of the substrate could be a key factor in understanding the kinetics of enzymes of similar characteristics.

  19. Kinetic investigation of heterogeneous catalytic reactions by means of the kinetic isotope method

    Energy Technology Data Exchange (ETDEWEB)

    Bauer, F; Dermietzel, J [Akademie der Wissenschaften der DDR, Leipzig. Zentralinstitut fuer Isotopen- und Strahlenforschung

    1978-09-01

    The application of the kinetic isotope method to heterogeneous catalytic processes is possible for surface compounds by using the steady-state relation. However, the characterization of intermediate products becomes ambiguous if sorption rates are of the same order of magnitude as surface reactions rates. The isotopic exchange reaction renders possible the estimation of sorption rates.

  20. Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms

    Science.gov (United States)

    Gao, Connie W.; Allen, Joshua W.; Green, William H.; West, Richard H.

    2016-06-01

    Reaction Mechanism Generator (RMG) constructs kinetic models composed of elementary chemical reaction steps using a general understanding of how molecules react. Species thermochemistry is estimated through Benson group additivity and reaction rate coefficients are estimated using a database of known rate rules and reaction templates. At its core, RMG relies on two fundamental data structures: graphs and trees. Graphs are used to represent chemical structures, and trees are used to represent thermodynamic and kinetic data. Models are generated using a rate-based algorithm which excludes species from the model based on reaction fluxes. RMG can generate reaction mechanisms for species involving carbon, hydrogen, oxygen, sulfur, and nitrogen. It also has capabilities for estimating transport and solvation properties, and it automatically computes pressure-dependent rate coefficients and identifies chemically-activated reaction paths. RMG is an object-oriented program written in Python, which provides a stable, robust programming architecture for developing an extensible and modular code base with a large suite of unit tests. Computationally intensive functions are cythonized for speed improvements.

  1. Deuterium secondary isotope kinetic effects in imine formation reactions

    International Nuclear Information System (INIS)

    Amaral, L. do; Rossi, M.H.

    1986-01-01

    The kinetic α-deuterium isotope effects, K D /K H , for reaction mechanisms is studied. The reaction of pH function to m-bromobenzaldehyde, semicarbazide nucleophile, methoxy-amine and hydroxylamine are analysed. (M.J.C.) [pt

  2. Reactions driving conformational movements (molecular motors) in gels: conformational and structural chemical kinetics.

    Science.gov (United States)

    Otero, Toribio F

    2017-01-18

    In this perspective the empirical kinetics of conducting polymers exchanging anions and solvent during electrochemical reactions to get dense reactive gels is reviewed. The reaction drives conformational movements of the chains (molecular motors), exchange of ions and solvent with the electrolyte and structural (relaxation, swelling, shrinking and compaction) gel changes. Reaction-driven structural changes are identified and quantified from electrochemical responses. The empirical reaction activation energy (E a ), the reaction coefficient (k) and the reaction orders (α and β) change as a function of the conformational energy variation during the reaction. This conformational energy becomes an empirical magnitude. E a , k, α and β include and provide quantitative conformational and structural information. The chemical kinetics becomes structural chemical kinetics (SCK) for reactions driving conformational movements of the reactants. The electrochemically stimulated conformational relaxation model describes empirical results and some results from the literature for biochemical reactions. In parallel the development of an emerging technological world of soft, wet, multifunctional and biomimetic tools and anthropomorphic robots driven by reactions of the constitutive material, as in biological organs, can be now envisaged being theoretically supported by the kinetic model.

  3. Iteration scheme for implicit calculations of kinetic and equilibrium chemical reactions in fluid dynamics

    International Nuclear Information System (INIS)

    Ramshaw, J.D.; Chang, C.H.

    1995-01-01

    An iteration scheme for the implicit treatment of equilibrium chemical reactions in partial equilibrium flow has previously been described. Here we generalize this scheme to kinetic reactions as well as equilibrium reactions. This extends the applicability of the scheme to problems with kinetic reactions that are fast in regions of the flow field but slow in others. The resulting scheme thereby provides a single unified framework for the implicit treatment of an arbitrary number of coupled equilibrium and kinetic reactions in chemically reacting fluid flow. 10 refs., 2 figs

  4. Bench-scale Kinetics Study of Mercury Reactions in FGD Liquors

    Energy Technology Data Exchange (ETDEWEB)

    Gary Blythe; John Currie; David DeBerry

    2008-03-31

    This document is the final report for Cooperative Agreement DE-FC26-04NT42314, 'Kinetics Study of Mercury Reactions in FGD Liquors'. The project was co-funded by the U.S. DOE National Energy Technology Laboratory and EPRI. The objective of the project has been to determine the mechanisms and kinetics of the aqueous reactions of mercury absorbed by wet flue gas desulfurization (FGD) systems, and develop a kinetics model to predict mercury reactions in wet FGD systems. The model may be used to determine optimum wet FGD design and operating conditions to maximize mercury capture in wet FGD systems. Initially, a series of bench-top, liquid-phase reactor tests were conducted and mercury species concentrations were measured by UV/visible light spectroscopy to determine reactant and byproduct concentrations over time. Other measurement methods, such as atomic absorption, were used to measure concentrations of vapor-phase elemental mercury, that cannot be measured by UV/visible light spectroscopy. Next, a series of bench-scale wet FGD simulation tests were conducted. Because of the significant effects of sulfite concentration on mercury re-emission rates, new methods were developed for operating and controlling the bench-scale FGD experiments. Approximately 140 bench-scale wet FGD tests were conducted and several unusual and pertinent effects of process chemistry on mercury re-emissions were identified and characterized. These data have been used to develop an empirically adjusted, theoretically based kinetics model to predict mercury species reactions in wet FGD systems. The model has been verified in tests conducted with the bench-scale wet FGD system, where both gas-phase and liquid-phase mercury concentrations were measured to determine if the model accurately predicts the tendency for mercury re-emissions. This report presents and discusses results from the initial laboratory kinetics measurements, the bench-scale wet FGD tests, and the kinetics modeling

  5. Defect kinetics in spinels: Long-time simulations of MgAl2O4, MgGa2O4, and MgIn2O4

    International Nuclear Information System (INIS)

    Uberuaga, B. P.; Voter, A. F.; Sickafus, K. E.; Bacorisen, D.; Smith, Roger; Ball, J. A.; Grimes, R. W.

    2007-01-01

    Building upon work in which we examined defect production and stability in spinels, we now turn to defect kinetics. Using temperature accelerated dynamics (TAD), we characterize the kinetics of defects in three spinel oxides: magnesium aluminate MgAl 2 O 4 , magnesium gallate MgGa 2 O 4 , and magnesium indate MgIn 2 O 4 . These materials have varying tendencies to disorder on the cation sublattices. In order to understand chemical composition effects, we first examine defect kinetics in perfectly ordered, or normal, spinels, focusing on point defects on each sublattice. We then examine the role that cation disorder has on defect mobility. Using TAD, we find that disorder creates local environments which strongly trap point defects, effectively reducing their mobility. We explore the consequences of this trapping via kinetic Monte Carlo (KMC) simulations on the oxygen vacancy (V O ) in MgGa 2 O 4 , finding that V O mobility is directly related to the degree of inversion in the system

  6. Ion-neutral gas reactions in a collision/reaction cell in inductively coupled plasma mass spectrometry: Correlation of ion signal decrease to kinetic rate constants

    Energy Technology Data Exchange (ETDEWEB)

    Gray, Patrick J. [Trace Element Research Laboratory, School of Earth Sciences, The Ohio State University, 125 S. Oval Mall, Columbus, OH 43210 (United States); Department of Chemistry, The Ohio State University, 120 18th Avenue, Columbus, OH 43210 (United States); Olesik, John W., E-mail: olesik.2@osu.edu [Trace Element Research Laboratory, School of Earth Sciences, The Ohio State University, 125 S. Oval Mall, Columbus, OH 43210 (United States)

    2015-03-01

    Reaction gas flow rate dependent Ar{sub 2}{sup +} and Ar{sup +} signals are correlated to fundamental kinetic rate coefficients. A simple calculation, assuming that gas exits the reaction cell due only to effusion, is described to estimate the gas pressure in the reaction cell. The value of the product of the kinetic rate constant and the ion residence time in the reaction cell can be determined from experimental measurement of the decrease in an ion signal as a function of reaction gas flow rate. New kinetic rate constants are determined for the reaction of CH{sub 3}F with Ar{sup +} and Ar{sub 2}{sup +}. - Highlights: • How to determine pressure and the product of the kinetic rate constant times the ion residence time in reaction cell • Relate measured ICP-DRC-MS signals versus gas flow rate to kinetic rate constants measured previously using SIFT-MS • Describe how to determine previously unmeasured kinetic rate constants using ICP-DRC-MS.

  7. Spectator Ions ARE Important! A Kinetic Study of the Copper-Aluminum Displacement Reaction

    Science.gov (United States)

    Sobel, Sabrina G.; Cohen, Skyler

    2010-01-01

    Surprisingly, spectator ions are responsible for unexpected kinetics in the biphasic copper(II)-aluminum displacement reaction, with the rate of reaction dependent on the identity of the otherwise ignored spectator ions. Application of a published kinetic analysis developed for a reaction between a rotating Al disk and a Cu(II) ion solution to the…

  8. Complex Reaction Kinetics in Chemistry: A Unified Picture Suggested by Mechanics in Physics

    Directory of Open Access Journals (Sweden)

    Elena Agliari

    2018-01-01

    Full Text Available Complex biochemical pathways can be reduced to chains of elementary reactions, which can be described in terms of chemical kinetics. Among the elementary reactions so far extensively investigated, we recall the Michaelis-Menten and the Hill positive-cooperative kinetics, which apply to molecular binding and are characterized by the absence and the presence, respectively, of cooperative interactions between binding sites. However, there is evidence of reactions displaying a more complex pattern: these follow the positive-cooperative scenario at small substrate concentration, yet negative-cooperative effects emerge as the substrate concentration is increased. Here, we analyze the formal analogy between the mathematical backbone of (classical reaction kinetics in Chemistry and that of (classical mechanics in Physics. We first show that standard cooperative kinetics can be framed in terms of classical mechanics, where the emerging phenomenology can be obtained by applying the principle of least action of classical mechanics. Further, since the saturation function plays in Chemistry the same role played by velocity in Physics, we show that a relativistic scaffold naturally accounts for the kinetics of the above-mentioned complex reactions. The proposed formalism yields to a unique, consistent picture for cooperative-like reactions and to a stronger mathematical control.

  9. Unravelling the Maillard reaction network by multiresponse kinetic modelling

    NARCIS (Netherlands)

    Martins, S.I.F.S.

    2003-01-01

    The Maillard reaction is an important reaction in food industry. It is responsible for the formation of colour and aroma, as well as toxic compounds as the recent discovered acrylamide. The knowledge of kinetic parameters, such as rate constants and activation energy, is necessary to predict its

  10. Kinetic modeling and fitting software for interconnected reaction schemes: VisKin.

    Science.gov (United States)

    Zhang, Xuan; Andrews, Jared N; Pedersen, Steen E

    2007-02-15

    Reaction kinetics for complex, highly interconnected kinetic schemes are modeled using analytical solutions to a system of ordinary differential equations. The algorithm employs standard linear algebra methods that are implemented using MatLab functions in a Visual Basic interface. A graphical user interface for simple entry of reaction schemes facilitates comparison of a variety of reaction schemes. To ensure microscopic balance, graph theory algorithms are used to determine violations of thermodynamic cycle constraints. Analytical solutions based on linear differential equations result in fast comparisons of first order kinetic rates and amplitudes as a function of changing ligand concentrations. For analysis of higher order kinetics, we also implemented a solution using numerical integration. To determine rate constants from experimental data, fitting algorithms that adjust rate constants to fit the model to imported data were implemented using the Levenberg-Marquardt algorithm or using Broyden-Fletcher-Goldfarb-Shanno methods. We have included the ability to carry out global fitting of data sets obtained at varying ligand concentrations. These tools are combined in a single package, which we have dubbed VisKin, to guide and analyze kinetic experiments. The software is available online for use on PCs.

  11. Kinetics of ion/molecule reactions in Xe++acteone system

    International Nuclear Information System (INIS)

    Vinogradov, P.S.; Misharin, A.S.

    2002-01-01

    A reaction of Xe+ ion with acetone and subsequent transformations of the product ions at a buffer gas pressure (He) of 1.1 Torr were studied by the flow reactor technique mass spectrometry. A kinetic scheme describing the evolution of the ionic composition has been determined. The rate constants of the key reactions involved in the scheme have been evaluated. A channel of the production of acetone cation in A state in a charge transfer reaction was observed. A production of slowly reacting isomer of the acetone cation in secondary reactions was detected. Its product in the reaction with acetone is the 'nonprotonated dimer'. The kinetics of the production of ternary ions - ( CH 3 CO + CH 3 COCH 3 )(m/e=101), CH 3 COCH 3 H + (m/e=59) as well as the production of ions of the fourth generation ( CH 3 CO + (CH 3 COCH 3 ) 2 ) (m/e=159) and (CH 3 COCH 3 ) 2 H + was observed. CH 3 CO + ion (m/e=43) was found as the main reaction product. The main pathways scheme of ionic transformations is shown. (nevyjel)

  12. Glycerol acetals, kinetic study of the reaction between glycerol and formaldehyde

    International Nuclear Information System (INIS)

    Agirre, I.; Garcia, I.; Requies, J.; Barrio, V.L.; Gueemez, M.B.; Cambra, J.F.; Arias, P.L.

    2011-01-01

    The acetalization reaction between glycerol and formaldehyde using Amberlyst 47 acidic ion exchange resin was studied. These acetals can be obtained from renewable sources (bioalcohols and bioalcohol derived aldehydes) and seem to be good candidates for different applications such as oxygenated diesel additives. A preliminary kinetic study was performed in a batch stirred tank reactor studying the influence of different process parameters like temperature, feed composition and the stirring speed. A pseudo homogenous kinetic model able to explain the reaction mechanism was adjusted. Thus, the corresponding order of reaction was determined. Amberlyst 47 acidic ion exchange resin showed a fairly good behavior allowing 100% of selectivity towards acetals formation. However, the studied acetalization reaction showed high thermodynamic limitations achieving glycerol conversions around 50% using a stoichiometric feed ratio at 353 K. The product is a mixture of two isomers (1,3-Dioxan-5-ol and 1,3-dioxolane-4-methanol) and the conversion of 1,3-dioxolane-4-methanol into 1,3-Dioxan-5-ol was also observed. -- Highlights: → The reaction between glycerol and acetaldehyde shows thermodynamic limitations. → Amberlyst 47 ion exchange resins show 100% of selectivity. → A pseudo-homogeneous kinetic model is able to predict the reaction progress. → Isomerization reactions were observed from dioxalanes to dioxanes.

  13. An atomistic vision of the Mass Action Law: Prediction of carbon/oxygen defects in silicon

    Energy Technology Data Exchange (ETDEWEB)

    Brenet, G.; Timerkaeva, D.; Caliste, D.; Pochet, P. [CEA, INAC-SP2M, Atomistic Simulation Laboratory, F-38000 Grenoble (France); Univ. Grenoble Alpes, INAC-SP2M, L-Sim, F-38000 Grenoble (France); Sgourou, E. N.; Londos, C. A. [University of Athens, Solid State Physics Section, Panepistimiopolis Zografos, Athens 157 84 (Greece)

    2015-09-28

    We introduce an atomistic description of the kinetic Mass Action Law to predict concentrations of defects and complexes. We demonstrate in this paper that this approach accurately predicts carbon/oxygen related defect concentrations in silicon upon annealing. The model requires binding and migration energies of the impurities and complexes, here obtained from density functional theory (DFT) calculations. Vacancy-oxygen complex kinetics are studied as a model system during both isochronal and isothermal annealing. Results are in good agreement with experimental data, confirming the success of the methodology. More importantly, it gives access to the sequence of chain reactions by which oxygen and carbon related complexes are created in silicon. Beside the case of silicon, the understanding of such intricate reactions is a key to develop point defect engineering strategies to control defects and thus semiconductors properties.

  14. Bayesian experts in exploring reaction kinetics of transcription circuits.

    Science.gov (United States)

    Yoshida, Ryo; Saito, Masaya M; Nagao, Hiromichi; Higuchi, Tomoyuki

    2010-09-15

    Biochemical reactions in cells are made of several types of biological circuits. In current systems biology, making differential equation (DE) models simulatable in silico has been an appealing, general approach to uncover a complex world of biochemical reaction dynamics. Despite of a need for simulation-aided studies, our research field has yet provided no clear answers: how to specify kinetic values in models that are difficult to measure from experimental/theoretical analyses on biochemical kinetics. We present a novel non-parametric Bayesian approach to this problem. The key idea lies in the development of a Dirichlet process (DP) prior distribution, called Bayesian experts, which reflects substantive knowledge on reaction mechanisms inherent in given models and experimentally observable kinetic evidences to the subsequent parameter search. The DP prior identifies significant local regions of unknown parameter space before proceeding to the posterior analyses. This article reports that a Bayesian expert-inducing stochastic search can effectively explore unknown parameters of in silico transcription circuits such that solutions of DEs reproduce transcriptomic time course profiles. A sample source code is available at the URL http://daweb.ism.ac.jp/~yoshidar/lisdas/.

  15. A kinetic model for the glucose/glycine Maillard reaction pathways

    NARCIS (Netherlands)

    Martins, S.I.F.S.; Boekel, van M.A.J.S.

    2005-01-01

    A comprehensive kinetic model for the glucose/glycine Maillard reaction is proposed based on an approach called multiresponse kinetic modelling. Special attention was paid to reactants, intermediates and end products: -fructose, N-(1-deoxy--fructos-1-yl)-glycine (DFG), 1-deoxy-2,3-hexodiulose and

  16. 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

  17. Extension of a Kinetic-Theory Approach for Computing Chemical-Reaction Rates to Reactions with Charged Particles

    Science.gov (United States)

    Liechty, Derek S.; Lewis, Mark J.

    2010-01-01

    Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.

  18. Defect reactions on the phosphorus sublattice in low-temperature electron-irradiated InP

    International Nuclear Information System (INIS)

    Sibille, A.; Suski, J.

    1985-01-01

    This Rapid Communication describes several thermally or electronically stimulated defect reactions involving the dominant deep centers in low-temperature (25--300 K) electron-irradiated InP. Some of these reactions result in an increased concentration of the centers, thereby revealing the existence of a secondary production mechanism of the related defects. Low-energy irradiations allows one to select the type of the ejected atom (P) and gives direct evidence that only a phosphorus species, interstitial or vacancy, is involved in the creation-reaction-annealing events

  19. Kinetics of Single-Enzyme Reactions on Vesicles: Role of Substrate Aggregation

    Science.gov (United States)

    Zhdanov, Vladimir P.

    2015-03-01

    Enzymatic reactions occurring in vivo on lipid membranes can be influenced by various factors including macromolecular crowding in general and substrate aggregation in particular. In academic studies, the role of these factors can experimentally be clarified by tracking single-enzyme kinetics occurring on individual lipid vesicles. To extend the conceptual basis for such experiments, we analyze herein the corresponding kinetics mathematically with emphasis on the role of substrate aggregation. In general, the aggregation may occur on different length scales. Small aggregates may e.g. contain a few proteins or peptides while large aggregates may be mesoscopic as in the case of lipid domains which can be formed in the membranes composed of different lipids. We present a kinetic model describing comprehensively the effect of aggregation of the former type on the dependence of the reaction rate on substrate membrane concentration. The results obtained with physically reasonable parameters indicate that the aggregation-related deviations from the conventional Michaelis-Menten kinetics may be appreciable. Special Issue Comments: This theoretical article is focused on single-enzyme reactions occurring in parallel with substrate aggregation on individual vesicles. This subject is related to a few Special Issue articles concerning enzyme dynamics6,7 and function8 and mathematical aspects of stochastic kinetics.9

  20. Kinetics of elementary atom and radical reactions

    International Nuclear Information System (INIS)

    Gordon, R.J.

    1990-06-01

    During the past three years we have been working on four problems in the general area of gas phase kinetics and energy transfer of small molecules. These are: (1) measurements of the fine structure populations of ground state oxygen atoms produced in photodissociation reactions; (2) quenching of the Rydberg B ( 1 Σ + ) state of CO; (3) vibrational relaxation of highly excited molecules; and (4) kinetics of hydrogen molecules. The first two topics, which involve transitions between different electronic states of the parent molecule, are a departure from our previous research interests. In the accompanying renewal proposal we discuss plans to pursue these new topics vigorously during the coming year. The third topic is a continuation of our long interest in the energy dependence of the rates laws governing vibrational-to-translational energy transfer of molecules having large initial amounts of vibrational excitation. The final topic is a continuation of our studies of the reaction of O( 3 P) + H 2 . In this work we measured the rate constant for the reaction O( 3 P) with deuterium and also analyzed spectroscopically different sources of vibrationally excited hydrogen for possible future work. We discuss each of these four studies in the following sections

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2015-12-15

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

  2. Kinetics of elementary atom and radical reactions: Progress report

    International Nuclear Information System (INIS)

    Gordon, R.J.

    1986-01-01

    Our research program is concerned with the kinetics of elementary gas phase reactions and energy transfer involving polyatomic molecules. We report here on three ongoing projects: The reaction of oxygen atoms with hydrogen molecules, the electronic relaxation of NH radicals, and the vibrational relaxation of highly excited SF 6 molecules. 10 refs., 5 figs

  3. Kinetic study of the dehydration reaction of lithium sulfate monohydrate crystals using microscopy and modeling

    Energy Technology Data Exchange (ETDEWEB)

    Lan, Shuiquan [Department of Mechanical Engineering, Eindhoven University of Technology, Den Dolech 2, 5612AZ Eindhoven (Netherlands); Zondag, Herbert [Department of Mechanical Engineering, Eindhoven University of Technology, Den Dolech 2, 5612AZ Eindhoven (Netherlands); Energy research Center of the Netherlands – ECN, P.O. Box 1, 1755ZG Petten (Netherlands); Steenhoven, Anton van [Department of Mechanical Engineering, Eindhoven University of Technology, Den Dolech 2, 5612AZ Eindhoven (Netherlands); Rindt, Camilo, E-mail: c.c.m.rindt@tue.nl [Department of Mechanical Engineering, Eindhoven University of Technology, Den Dolech 2, 5612AZ Eindhoven (Netherlands)

    2015-12-10

    Highlights: • Kinetics of Li{sub 2}SO{sub 4}·H{sub 2}O single crystals were modeled based on elementary processes. • Kinetics of nucleation and nuclei growth were studied by using optical microscopy. • A novel experiment was designed to visualize the reaction front into crystal bulk. • Fractional conversion was calculated and compared with TGA-experiments. - Abstract: Simulation of gas–solid reactions occurring in industrial processes requires a robust kinetic model to be applicable in a wide range of complicated reaction conditions. However, in literature it is often seen that even the same reaction under specific controlled conditions is interpreted with different kinetic models. In the present work, a phenomenological model based on nucleation and nuclei growth processes is presented to study the kinetics of the dehydration reaction of lithium sulfate monohydrate single crystals. The two elementary processes of the reaction, nucleation and nuclei growth, are characterized and quantified as a function of temperature by using optical microscopy experiments. The in-situ measured characteristics of the dehydration reaction provided confirmatory evidence that the rate of nucleation obeys an exponential law and the rate of nuclei growth is approximately constant. With knowledge acquired from the optical observations as inputs of the kinetic model, the fractional conversion of the dehydration reaction was calculated and compared with experimental results from thermogravimetric analysis (TGA). A satisfactory comparison was found both in isothermal and non-isothermal conditions. It is demonstrated that this knowledge-based model has a great potential to represent the gas–solid reaction kinetics in a wide range of process conditions regarding temperature, pressure and particle geometry.

  4. Reaction kinetics, reaction products and compressive strength of ternary activators activated slag designed by Taguchi method

    NARCIS (Netherlands)

    Yuan, B.; Yu, Q.L.; Brouwers, H.J.H.

    2015-01-01

    This study investigates the reaction kinetics, the reaction products and the compressive strength of slag activated by ternary activators, namely waterglass, sodium hydroxide and sodium carbonate. Nine mixtures are designed by the Taguchi method considering the factors of sodium carbonate content

  5. Reaction kinetics of cellulose hydrolysis in subcritical and supercritical water

    Science.gov (United States)

    Olanrewaju, Kazeem Bode

    The uncertainties in the continuous supply of fossil fuels from the crisis-ridden oil-rich region of the world is fast shifting focus on the need to utilize cellulosic biomass and develop more efficient technologies for its conversion to fuels and chemicals. One such technology is the rapid degradation of cellulose in supercritical water without the need for an enzyme or inorganic catalyst such as acid. This project focused on the study of reaction kinetics of cellulose hydrolysis in subcritical and supercritical water. Cellulose reactions at hydrothermal conditions can proceed via the homogeneous route involving dissolution and hydrolysis or the heterogeneous path of surface hydrolysis. The work is divided into three main parts. First, the detailed kinetic analysis of cellulose reactions in micro- and tubular reactors was conducted. Reaction kinetics models were applied, and kinetics parameters at both subcritical and supercritical conditions were evaluated. The second major task was the evaluation of yields of water soluble hydrolysates obtained from the hydrolysis of cellulose and starch in hydrothermal reactors. Lastly, changes in molecular weight distribution due to hydrothermolytic degradation of cellulose were investigated. These changes were also simulated based on different modes of scission, and the pattern generated from simulation was compared with the distribution pattern from experiments. For a better understanding of the reaction kinetics of cellulose in subcritical and supercritical water, a series of reactions was conducted in the microreactor. Hydrolysis of cellulose was performed at subcritical temperatures ranging from 270 to 340 °C (tau = 0.40--0.88 s). For the dissolution of cellulose, the reaction was conducted at supercritical temperatures ranging from 375 to 395 °C (tau = 0.27--0.44 s). The operating pressure for the reactions at both subcritical and supercritical conditions was 5000 psig. The results show that the rate-limiting step in

  6. Photocatalytic Water-Splitting Reaction from Catalytic and Kinetic Perspectives

    KAUST Repository

    Hisatomi, Takashi

    2014-10-16

    Abstract: Some particulate semiconductors loaded with nanoparticulate catalysts exhibit photocatalytic activity for the water-splitting reaction. The photocatalysis is distinct from the thermal catalysis because photocatalysis involves photophysical processes in particulate semiconductors. This review article presents a brief introduction to photocatalysis, followed by kinetic aspects of the photocatalytic water-splitting reaction.Graphical Abstract: [Figure not available: see fulltext.

  7. Kinetics of heterogeneous catalytic reactions

    CERN Document Server

    Boudart, Michel

    2014-01-01

    This book is a critical account of the principles of the kinetics of heterogeneous catalytic reactions in the light of recent developments in surface science and catalysis science. Originally published in 1984. The Princeton Legacy Library uses the latest print-on-demand technology to again make available previously out-of-print books from the distinguished backlist of Princeton University Press. These paperback editions preserve the original texts of these important books while presenting them in durable paperback editions. The goal of the Princeton Legacy Library is to vastly increase acc

  8. Non-equilibrium reaction rates in chemical kinetic equations

    Science.gov (United States)

    Gorbachev, Yuriy

    2018-05-01

    Within the recently proposed asymptotic method for solving the Boltzmann equation for chemically reacting gas mixture, the chemical kinetic equations has been derived. Corresponding one-temperature non-equilibrium reaction rates are expressed in terms of specific heat capacities of the species participate in the chemical reactions, bracket integrals connected with the internal energy transfer in inelastic non-reactive collisions and energy transfer coefficients. Reactions of dissociation/recombination of homonuclear and heteronuclear diatomic molecules are considered. It is shown that all reaction rates are the complex functions of the species densities, similarly to the unimolecular reaction rates. For determining the rate coefficients it is recommended to tabulate corresponding bracket integrals, additionally to the equilibrium rate constants. Correlation of the obtained results with the irreversible thermodynamics is established.

  9. A kinetic study on non-catalytic reactions in hydroprocessing Boscan crude oil

    Energy Technology Data Exchange (ETDEWEB)

    A. Marafi; E. Kam; A. Stanislaus [Kuwait Institute for Scientific Research, Safat (Kuwait). Petroleum Refining Department, Petroleum Research and Studies Center

    2008-08-15

    Non-catalytic hydrothermal cracking reactions are known to associate with catalytic hydrocracking reactions. In a recent study on hydroprocessing of Boscan crude over a specific catalyst system containing three distinct catalysts, it was found that hydrodesulfurization (HDS) and hydrodemetallation (HDM) reactions continued even when the catalyst is severely deactivated. Since the reactor was packed with considerable amount of inert material besides the three catalysts, it will be advantage to determine if the inert materials can also facilitate hydroprocessing reactions. A series of kinetic experiments for the inert particles was undertaken under different space velocity and temperature conditions. The extent of catalytic and non-catalytic hydroprocessing reactions was assessed. Through statistical analysis, the initial reaction rate constant, reaction order and activation energy for various hydroprocessing reactions were then determined. The absolute average deviations (AAD) of the kinetics values obtained for inert materials are less than 10%. 25 refs., 7 figs., 4 tabs.

  10. Kinetics of catalytic reactions solutions manual

    CERN Document Server

    Vannice, M Albert

    2005-01-01

    Including countless exercises and worked examples, this advanced reference work and textbook will be extremely useful for the work of many industrial scientists. It teaches readers to design kinetic experiments involving heterogeneous catalysts, to characterize these catalysts, to acquire rate data, to find heat and mass transfer limitations in these data, to select reaction models, to derive rate expressions based on these models, and to assess the consistency of these rate equations.

  11. Mechanistic rationalization of unusual sigmoidal kinetic profiles in the Machetti-De Sarlo cycloaddition reaction.

    Science.gov (United States)

    Mower, Matthew P; Blackmond, Donna G

    2015-02-18

    Unusual sigmoidal kinetic profiles in the Machetti-De Sarlo base-catalyzed 1,3-dipolar cycloaddition of acrylamide to N-methylnitroacetamide are rationalized by detailed in situ kinetic analysis. A dual role is uncovered in which a substrate acts as a precursor to catalyze its own reaction. Such kinetic studies provide a general protocol for distinguishing among different mechanistic origins of induction periods in complex organic reactions.

  12. Stability and kinetics of point defects in SiO2 and in SiC

    International Nuclear Information System (INIS)

    Roma, G.

    2012-01-01

    This document is conceived as an overview of Guido Roma's research achievements on defects stability and kinetics in two materials of interest in nuclear science and for many other application domains: silicon dioxide and silicon carbide. An extended summary in french is followed by the main document, in english. Chapter 1 describes the context, introduces the approach and explains the choice of silicon dioxide and silicon carbide. Chapter 2 discusses several approximations and specific issues of the application of Density Functional Theory to point defects in non-metallic materials for the study of defects energetics and diffusion. Chapter 3 is devoted to native defects in silicon dioxide and the understanding of self-diffusion in crystalline and amorphous SiO 2 . Chapter 4 summarises the results on native defects and palladium impurities in silicon carbide. A conclusion, including suggestions for future developments, closes the main part of the document. (author) [fr

  13. 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

  14. Kinetics Analysis of Synthesis Reaction of Struvite With Air-Flow Continous Vertical Reactors

    Science.gov (United States)

    Edahwati, L.; Sutiyono, S.; Muryanto, S.; Jamari, J.; Bayuseno, dan A. P.

    2018-01-01

    Kinetics reaction is a knowledge about a rate of chemical reaction. The differential of the reaction rate can be determined from the reactant material or the formed material. The reaction mechanism of a reactor may include a stage of reaction occurring sequentially during the process of converting the reactants into products. In the determination of reaction kinetics, the order of reaction and the rate constant reaction must be recognized. This study was carried out using air as a stirrer as a medium in the vertical reactor for crystallization of struvite. Stirring is one of the important aspects in struvite crystallization process. Struvite crystals or magnesium ammonium phosphate hexahydrates (MgNH4PO4·6H2O) is commonly formed in reversible reactions and can be generated as an orthorhombic crystal. Air is selected as a stirrer on the existing flow pattern in the reactor determining the reaction kinetics of the crystal from the solution. The experimental study was conducted by mixing an equimolar solution of 0.03 M NH4OH, MgCl2 and H3PO4 with a ratio of 1: 1: 1. The crystallization process of the mixed solution was observed in an inside reactor at the flow rate ranges of 16-38 ml/min and the temperature of 30°C was selected in the study. The air inlet rate was kept constant at 0.25 liters/min. The pH solution was adjusted to be 8, 9 and 10 by dropping wisely of 1 N KOH solution. The crystallization kinetics was examined until the steady state of the reaction was reached. The precipitates were filtered and dried at a temperature for subsequent material characterization, including Scanning Electron Microscope (SEM) and XRD (X-Ray diffraction) method. The results show that higher flow rate leads to less mass of struvite.

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

    International Nuclear Information System (INIS)

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

    2011-01-01

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

  16. 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)

  17. A kinetic reaction model for biomass pyrolysis processes in Aspen Plus

    International Nuclear Information System (INIS)

    Peters, Jens F.; Banks, Scott W.; Bridgwater, Anthony V.; Dufour, Javier

    2017-01-01

    Highlights: • Predictive kinetic reaction model applicable to any lignocellulosic feedstock. • Calculates pyrolysis yields and product composition as function of reactor conditions. • Detailed modelling of product composition (33 model compounds for the bio-oil). • Good agreement with literature regarding yield curves and product composition. • Successful validation with pyrolysis experiments in bench scale fast pyrolysis rig. - Abstract: This paper presents a novel kinetic reaction model for biomass pyrolysis processes. The model is based on the three main building blocks of lignocellulosic biomass, cellulose, hemicellulose and lignin and can be readily implemented in Aspen Plus and easily adapted to other process simulation software packages. It uses a set of 149 individual reactions that represent the volatilization, decomposition and recomposition processes of biomass pyrolysis. A linear regression algorithm accounts for the secondary pyrolysis reactions, thus allowing the calculation of slow and intermediate pyrolysis reactions. The bio-oil is modelled with a high level of detail, using up to 33 model compounds, which allows for a comprehensive estimation of the properties of the bio-oil and the prediction of further upgrading reactions. After showing good agreement with existing literature data, our own pyrolysis experiments are reported for validating the reaction model. A beech wood feedstock is subjected to pyrolysis under well-defined conditions at different temperatures and the product yields and compositions are determined. Reproducing the experimental pyrolysis runs with the simulation model, a high coincidence is found for the obtained fraction yields (bio-oil, char and gas), for the water content and for the elemental composition of the pyrolysis products. The kinetic reaction model is found to be suited for predicting pyrolysis yields and product composition for any lignocellulosic biomass feedstock under typical pyrolysis conditions

  18. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    Energy Technology Data Exchange (ETDEWEB)

    Gorman, Brian P [Colorado School of Mines, Golden, CO (United States)

    2015-09-02

    Project Description: The general objective of the proposed research is to determine the kinetics and mechanisms of calcite reactions with saline waters over a wide range of saline water composition, pCO2, and modest ranges in T and P. This will be accomplished by studying both reaction rates and solubility from changes in solution chemistry, and making nanoscale observations of calcite precipitate surface morphology and composition at the micro-to-nano-scale to provide an understanding of controlling reaction mechanisms and pathways. The specific objectives necessary to reach the general objective are: a) determination of how pCO2, Ca2+, ionic strength and “foreign” ions influence reaction rates; and b) investigate the influence of these parameters on apparent kinetic solubility from dissolution and precipitation reactions. This information will clearly be central to the construction of reliable reaction-transport models to predict reservoir and formation response to increased CO2 in saline waters. This program was initially collaborative with John Morse at Texas A&M, however his passing shortly after the beginning of this program resulted in abbreviated research time and effort. Summary of Results: Early studies using electron microscopy and spectroscopy indicated that carbonate precipitation from natural seawater (NSW) conditions onto aragonite substrates was mediated by a surface amorphous calcium carbonate layer. It was hypothesized that this ACC layer (observed after < 5days reaction time) was responsible for the abnormal reaction kinetics and also served as a metastable seed layer for growth of epitaxial aragonite. Further studies of the ACC formation mechanism indicated a strong dependence on the Mg concentration in solution. Subsequent studies at shorter times (10 hrs) on calcite substrates and in a wide range of supersaturation conditions did not indicate any ACC layer. Instead, an epitaxial layer by layer

  19. Reaction kinetics of dolomite rim growth

    Science.gov (United States)

    Helpa, V.; Rybacki, E.; Abart, R.; Morales, L. F. G.; Rhede, D.; Jeřábek, P.; Dresen, G.

    2014-04-01

    Reaction rims of dolomite (CaMg[CO3]2) were produced by solid-state reactions at the contacts of oriented calcite (CaCO3) and magnesite (MgCO3) single crystals at 400 MPa pressure, 750-850 °C temperature, and 3-146 h annealing time to determine the reaction kinetics. The dolomite reaction rims show two different microstructural domains. Elongated palisades of dolomite grew perpendicular into the MgCO3 interface with length ranging from about 6 to 41 µm. At the same time, a 5-71 µm wide rim of equiaxed granular dolomite grew at the contact with CaCO3. Platinum markers showed that the original interface is located at the boundary between the granular and palisade-forming dolomite. In addition to dolomite, a 12-80 µm thick magnesio-calcite layer formed between the dolomite reaction rims and the calcite single crystals. All reaction products show at least an axiotactic crystallographic relationship with respect to calcite reactant, while full topotaxy to calcite prevails within the granular dolomite and magnesio-calcite. Dolomite grains frequently exhibit growth twins characterized by a rotation of 180° around one of the equivalent axis. From mass balance considerations, it is inferred that the reaction rim of dolomite grew by counter diffusion of MgO and CaO. Assuming an Arrhenius-type temperature dependence, activation energies for diffusion of CaO and MgO are E a (CaO) = 192 ± 54 kJ/mol and E a (MgO) = 198 ± 44 kJ/mol, respectively.

  20. Model of defect reactions and the influence of clustering in pulse-neutron-irradiated Si

    International Nuclear Information System (INIS)

    Myers, S. M.; Cooper, P. J.; Wampler, W. R.

    2008-01-01

    Transient reactions among irradiation defects, dopants, impurities, and carriers in pulse-neutron-irradiated Si were modeled taking into account the clustering of the primal defects in recoil cascades. Continuum equations describing the diffusion, field drift, and reactions of relevant species were numerically solved for a submicrometer spherical volume, within which the starting radial distributions of defects could be varied in accord with the degree of clustering. The radial profiles corresponding to neutron irradiation were chosen through pair-correlation-function analysis of vacancy and interstitial distributions obtained from the binary-collision code MARLOWE, using a spectrum of primary recoil energies computed for a fast-burst fission reactor. Model predictions of transient behavior were compared with a variety of experimental results from irradiated bulk Si, solar cells, and bipolar-junction transistors. The influence of defect clustering during neutron bombardment was further distinguished through contrast with electron irradiation, where the primal point defects are more uniformly dispersed

  1. Kinetics of the epoxy–thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components

    International Nuclear Information System (INIS)

    Loureiro, Roi Meizoso; Amarelo, Tánia Carballeira; Abuin, Senen Paz; Soulé, Ezequiel R.; Williams, Roberto J.J.

    2015-01-01

    Graphical abstract: - Highlights: • Reaction kinetics of a monoepoxy and a monothiol was studied by DSC. • Benzyldimethylamine (BDMA) was used as initiator. • Reaction exhibited a long induction period followed by a fast autocatalytic rate. • A mechanistic kinetic model provided a reasonable fitting of the kinetic behavior. • The formulation simulates the behavior of room-temperature-cure commercial epoxies. - Abstract: An analysis of the kinetics of the epoxy–thiol reaction in a model stoichiometric system of monofunctional reagents, 3-mercaptopropionate (BMP) and phenylglycidylether (PGE) is reported. Benzyldimethylamine (BDMA) was employed as initiator in amounts ranging from 0.5 to 2 wt%. These formulations showed a kinetic behavior qualitatively similar to that of commercial adhesives and coatings formulated for a room-temperature cure. Isothermal DSC scans revealed the existence of a relatively long induction period preceding a fast autocatalytic reaction step. Dynamic DSC scans showed that the reaction was shifted to a lower temperature range by increasing the storage period of the initial formulation at 20 °C. This unusual kinetic behavior could be modeled assuming that thiolate anions, slowly generated during the induction period, initiated a fast autocatalytic propagation/proton transfer reaction. The kinetic model included a pseudo-steady state for the initiator concentration and an equilibrium reaction between epoxy and OH groups generated by reaction. A reasonable fitting of isothermal and dynamic DSC runs was achieved in a broad range of temperatures and amine concentrations. In particular, both the length of the induction time and the effect of the storage period were correctly predicted

  2. Kinetics of the epoxy–thiol click reaction initiated by a tertiary amine: Calorimetric study using monofunctional components

    Energy Technology Data Exchange (ETDEWEB)

    Loureiro, Roi Meizoso; Amarelo, Tánia Carballeira [Gairesa, Outeiro 1, Lago (Valdoviño), 15551 A Coruña (Spain); Abuin, Senen Paz, E-mail: senen@gairesa.com [Gairesa, Outeiro 1, Lago (Valdoviño), 15551 A Coruña (Spain); Soulé, Ezequiel R. [Institute of Materials Science and Technology (INTEMA), University of Mar del Plata and National Research Council (CONICET), J. B. Justo 4302, 7600 Mar del Plata (Argentina); Williams, Roberto J.J., E-mail: williams@fi.mdp.edu.ar [Institute of Materials Science and Technology (INTEMA), University of Mar del Plata and National Research Council (CONICET), J. B. Justo 4302, 7600 Mar del Plata (Argentina)

    2015-09-20

    Graphical abstract: - Highlights: • Reaction kinetics of a monoepoxy and a monothiol was studied by DSC. • Benzyldimethylamine (BDMA) was used as initiator. • Reaction exhibited a long induction period followed by a fast autocatalytic rate. • A mechanistic kinetic model provided a reasonable fitting of the kinetic behavior. • The formulation simulates the behavior of room-temperature-cure commercial epoxies. - Abstract: An analysis of the kinetics of the epoxy–thiol reaction in a model stoichiometric system of monofunctional reagents, 3-mercaptopropionate (BMP) and phenylglycidylether (PGE) is reported. Benzyldimethylamine (BDMA) was employed as initiator in amounts ranging from 0.5 to 2 wt%. These formulations showed a kinetic behavior qualitatively similar to that of commercial adhesives and coatings formulated for a room-temperature cure. Isothermal DSC scans revealed the existence of a relatively long induction period preceding a fast autocatalytic reaction step. Dynamic DSC scans showed that the reaction was shifted to a lower temperature range by increasing the storage period of the initial formulation at 20 °C. This unusual kinetic behavior could be modeled assuming that thiolate anions, slowly generated during the induction period, initiated a fast autocatalytic propagation/proton transfer reaction. The kinetic model included a pseudo-steady state for the initiator concentration and an equilibrium reaction between epoxy and OH groups generated by reaction. A reasonable fitting of isothermal and dynamic DSC runs was achieved in a broad range of temperatures and amine concentrations. In particular, both the length of the induction time and the effect of the storage period were correctly predicted.

  3. Deviation from the kinetic law of mass action for reactions induced by binary encounters in liquid solutions

    International Nuclear Information System (INIS)

    Doktorov, Alexander B; Kipriyanov, Alexey A

    2007-01-01

    In considering the irreversible chemical reaction A+B→ C+B in liquid solutions two many-particle approaches to the derivation of binary non-Markovian kinetic equations are compared: simple superposition decoupling and a method of extracting 'pair' channels from three-particle correlation evolution. It is shown that both methods provide an almost identical description of this reaction. However, in studies of reversible reactions in liquid solutions only the channel extraction method gives a correct physically clear description of the reaction though it consists of a sequence of steps: the development of integral encounter theory (IET), effective pairs approximation (EPA), modified encounter theory (MET), and the final regular form (RF) of kinetic equations. It is shown that the rate equations often encountered in the literature correspond to the independence of transient channels of 'scattering' in the bimolecular reversible reaction (A+B -B), while the independent transient channel of 'decay' in the reversible reactionA+B -C is defined solely by time integral convolution. In the general case transient channels in non-Markovian theory are not independent, and their interference manifests itself as a non-Markovian inhomogeneous source in binary non-Markovian kinetic equations in regular form. Based on the derived equations new universal kinetics (independent of models) of chemical equilibrium attainment have been obtained. It is shown that these kinetics can differ essentially from the kinetics corresponding to the kinetic law of mass action of formal chemical kinetics

  4. Kinetics of the Coupled Gas-Iron Reactions Involving Silicon and ...

    African Journals Online (AJOL)

    The kinetic study of coupled gas-iron reactions at 15600 has been carried out for the system involving liquid iron containing carbon and silicon and a gas phase consisting carbon monoxide, silicon monoxide and carbon dioxide. The coupled reactions are: (1) 200(g) = CO2 + C. (2) SiO (g) + CO (g) = Si ¸ CO (g). (3) SiO (g) + ...

  5. An investigation of the general regularity of size dependence of reaction kinetics of nanoparticles

    International Nuclear Information System (INIS)

    Cui, Zixiang; Duan, Huijuan; Xue, Yongqiang; Li, Ping

    2015-01-01

    In the processes of preparation and application of nanomaterials, the chemical reactions of nanoparticles are often involved, and the size of nanoparticles has dramatic influence on the reaction kinetics. Nevertheless, there are many conflicts on regularities of size dependence of reaction kinetic parameters, and these conflicts have not been explained so far. In this paper, taking the reaction of nano-ZnO (average diameter is from 20.96 to 53.31 nm) with acrylic acid solution as a system, the influence regularities of the particle size on the kinetic parameters were researched. The regularities were consistent with that in most literatures, but inconsistent with that in a few of literatures, the reasons for the conflicts were interpreted. The reasons can be attributed to two factors: one is improper data processing for fewer data points, and the other is the difference between solid particles and porous particles. A general regularity of the size dependence of reaction kinetics for solid particles was obtained. The regularity shows that with the size of nanoparticles decreasing, the rate constant and the reaction order increase, while the apparent activation energy and the pre-exponential factor decrease; and the relationships of the logarithm of rate constant, the logarithm of pre-exponential factor, and the apparent activation energy to the reciprocal of the particle size are linear, respectively

  6. CuInSe2 nano-crystallite reaction kinetics using solid state reaction from Cu2Se and In2Se3 powders

    International Nuclear Information System (INIS)

    Hsiang, Hsing-I; Lu, Li-Hsin; Chang, Yu-Lun; Ray, Dahtong; Yen, Fu-Su

    2011-01-01

    Highlights: → CuInSe 2 phase increased gradually accompanied with a decrease in γ-In 2 Se 3 and no intermediate phase during calcination. → CuInSe 2 formation from Cu 2 Se and In 2 Se 3 powders follows a one-dimensional diffusion-controlled reaction with apparent activation energy of about 122.5 kJ/mol. → The solid reaction kinetics may be dominated by the diffusion of In 3+ ions. - Abstract: The reaction mechanism and CuInSe 2 formation kinetics using a solid state reaction from Cu 2 Se and In 2 Se 3 powders synthesized using a heating up process were investigated using X-ray diffractomy (XRD) and transmission electron microscopy (TEM). It was observed that the CuInSe 2 phase increased gradually, accompanied with a decrease in γ-In 2 Se 3 with no intermediate phase as the calcination temperature and soaking time were increased. The reaction kinetics was analyzed using the Avrami and polynomial kinetic model, suggesting that CuInSe 2 formation from Cu 2 Se and In 2 Se 3 powders follows a diffusion-controlled reaction with an apparent activation energy of about 122.5-182.3 kJ/mol. Cu 2 Se and In 2 Se 3 phases react and directly transform into CIS without the occurrence of any intermediate phase and the size of the newly formed CuInSe 2 crystallites was close to that of the Cu 2 Se reactant particle based on the TEM results, which indicated that the solid reaction kinetics may be dominated by the diffusion of In 3+ ions.

  7. Isothermal reaction calorimetry as a tool for kinetic analysis

    International Nuclear Information System (INIS)

    Zogg, Andreas; Stoessel, Francis; Fischer, Ulrich; Hungerbuehler, Konrad

    2004-01-01

    Reaction calorimetry has found widespread application for thermal and kinetic analysis of chemical reactions in the context of thermal process safety as well as process development. This paper reviews the most important reaction calorimetric principles (heat-flow, heat-balance, power-compensation, and Peltier principle) and their applications in commercial or scientific devices. The discussion focuses on the different dynamic behavior of the main calorimetric principles during an isothermal reaction measurement. Examples of available reaction calorimeters are further compared considering their detection limit, time constant as well as temperature range. In a second part, different evaluation methods for the isothermally measured calorimetric data are reviewed and discussed. The methods will be compared, focusing especially on the fact that reaction calorimetric data always contains additional informations not directly related to the actual chemical reaction such as heat of mixing, heat of phase-transfer/change processes or simple measurement errors. Depending on the evaluation method applied such disturbances have a significant influence on the calculated reaction enthalpies or rate constants

  8. Oxidation Kinetics of Copper: An Experiment in Solid State Chemistry.

    Science.gov (United States)

    Ebisuzaki, Y.; Sanborn, W. B.

    1985-01-01

    Oxidation kinetics in metals and the role defects play in diffusion-controlled reactions are discussed as background for a junior/senior-level experiment in the physical or inorganic chemistry laboratory. Procedures used and typical data obtained are provided for the experiment. (JN)

  9. Kinetics of the Br2-CH3CHO Photochemical Chain Reaction

    Science.gov (United States)

    Nicovich, J. M.; Shackelford, C. J.; Wine, P. H.

    1997-01-01

    Time-resolved resonance fluorescence spectroscopy was employed in conjunction with laser flash photolysis of Br2 to study the kinetics of the two elementary steps in the photochemical chain reaction nBr2 + nCH3CHO + hv yields nCH3CBrO + nHBr. In the temperature range 255-400 K, the rate coefficient for the reaction Br((sup 2)P(sub 3/2)) + CH3CHO yields CH3CO + HBr is given by the Arrhenius expression k(sub 6)(T) = (1.51 +/- 0.20) x 10(exp -11) exp(-(364 +/- 41)/T)cu cm/(molecule.s). At 298 K, the reaction CH3CO + Br2 yields CH3CBrO + Br proceeds at a near gas kinetic rate, k(sub 7)(298 K) = (1.08 +/- 0.38) x 10(exp -10)cu cm/(molecule.s).

  10. Reaction kinetics of resveratrol with thiyl and alkoxyl radicals

    International Nuclear Information System (INIS)

    Dzeba, I.; Mihaljevic, B.

    2011-01-01

    Complete text of publication follows. Plant derived resveratrol (trans-3,5,4'-trihydroxystilbene) possesses a broad spectrum of biological activities, one of them are very well known its antioxidative properties. Our work aims to provide kinetic data with regard to the reactivity of resveratrol with uninvestigated short-lived bioradicals, identified as mediators in oxidative lipid degradation processes. Radicals of our interest are alkoxyl radicals, well known propagators of the chain free radical reactions in lipids, and thiyl radicals which protect lipids from their degradation pathway, but at the same time cause the isomerization of the double bonds. In order to investigate these reactions of resveratrol laser flash photolysis was used. On the basis of competitive kinetics the rate constants were determined under pseudo-first order conditions in acetonitrile solutions at room temperature. Thiyl radicals were generated indirectly in solution containing 1-octadecanthiol and photosensitive benzophenone in acetonitrile using the light pulses at 347 nm from ruby laser. Tert-butoxyl radicals were generated directly by peroxide bond cleavage from di-tert-butyl peroxide in acetonitrile by light pulses of Nd:YAG at 355 nm, and ruby at 347 nm. Obtained rate constants for the reactions of resveratrol and radicals generated by laser flash photolysis will be summarized and compared with rare literature data for the rate constants of investigated reactions of resveratrol and other radicals generated by pulse radiolysis.

  11. Model for transport and reaction of defects and carriers within displacement cascades in gallium arsenide

    International Nuclear Information System (INIS)

    Wampler, William R.; Myers, Samuel M.

    2015-01-01

    A model is presented for recombination of charge carriers at evolving displacement damage in gallium arsenide, which includes clustering of the defects in atomic displacement cascades produced by neutron or ion irradiation. The carrier recombination model is based on an atomistic description of capture and emission of carriers by the defects with time evolution resulting from the migration and reaction of the defects. The physics and equations on which the model is based are presented, along with the details of the numerical methods used for their solution. The model uses a continuum description of diffusion, field-drift and reaction of carriers, and defects within a representative spherically symmetric cluster of defects. The initial radial defect profiles within the cluster were determined through pair-correlation-function analysis of the spatial distribution of defects obtained from the binary-collision code MARLOWE, using recoil energies for fission neutrons. Properties of the defects are discussed and values for their parameters are given, many of which were obtained from density functional theory. The model provides a basis for predicting the transient response of III-V heterojunction bipolar transistors to displacement damage from energetic particle irradiation

  12. Kinetics of reactions of aquacobalamin with aspartic and glutamic acids and their amides in water solutions

    Science.gov (United States)

    Bui, T. T. T.; Sal'nikov, D. S.; Dereven'kov, I. A.; Makarov, S. V.

    2017-04-01

    The kinetics of aquacobalamin reaction with aspartic and glutamic acids, and with their amides in water solutions, is studied via spectrophotometry. The kinetic and activation parameters of the process are determined. It is shown that the reaction product is cobalamin-amino acid complex. The data are compared to results on the reaction between aquacobalamin and primary amines.

  13. Thermodynamic and kinetic modelling of fuel oxidation behaviour in operating defective fuel

    International Nuclear Information System (INIS)

    Lewis, B.J.; Thompson, W.T.; Akbari, F.; Thompson, D.M.; Thurgood, C.; Higgs, J.

    2004-01-01

    A theoretical treatment has been developed to predict the fuel oxidation behaviour in operating defective nuclear fuel elements. The equilibrium stoichiometry deviation in the hyper-stoichiometric fuel has been derived from thermodynamic considerations using a self-consistent set of thermodynamic properties for the U-O system, which emphasizes replication of solubilities and three-phase invariant conditions displayed in the U-O binary phase diagram. The kinetics model accounts for multi-phase transport including interstitial oxygen diffusion in the solid and gas-phase transport of hydrogen and steam in the fuel cracks. The fuel oxidation model is further coupled to a heat conduction model to account for the feedback effect of a reduced thermal conductivity in the hyper-stoichiometric fuel. A numerical solution has been developed using a finite-element technique with the FEMLAB software package. The model has been compared to available data from several in-reactor X-2 loop experiments with defective fuel conducted at the Chalk River Laboratories. The model has also been benchmarked against an O/U profile measurement for a spent defective fuel element discharged from a commercial reactor

  14. Kinetics of interstitial defects in α-Fe: The effect from uniaxial stress

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Changwoo [Department of Nuclear Engineering, Texas A& M University, College Station, TX 77843 (United States); Wang, Qingyu [College of Nuclear Science and Technology, Harbin Engineering University, Harbin 150001 (China); Shao, Lin, E-mail: lshao@tamu.edu [Department of Nuclear Engineering, Texas A& M University, College Station, TX 77843 (United States)

    2017-03-15

    Understanding defect kinetics in a stress field is important for multiscale modeling of materials degradation of nuclear materials. By means of molecular dynamics and molecular statics simulations, we calculate formation and migration energies of self-interstitial atoms (SIA) and SIA clusters (up to size of 5 interstitials) in alpha Fe and identify their stable configurations under uniaxial tensile strains. By applying uniaxial stress along [111], <111> oriented single SIA defects become more stable than <110> oriented SIA, which is opposite to stress-free condition. Diffusion of single SIA defects under [111] tensile stress is facilitated along [111] direction and the diffusion becomes one dimensional (1D). For SIA clusters, their diffusion under zero stress has gradual transition from three dimensional (3D) for small clusters to one dimensional (1D) for large clusters. Under the tensile stress along [111], the 3D to 1D transition is accelerated. For large SIA clusters, the stress effect is quickly saturated with less diffusivity enhancement in comparison with small SIA clusters.

  15. Strain-induced structural changes and chemical reactions. 1: Thermomechanical and kinetic models

    International Nuclear Information System (INIS)

    Levitas, V.I.; Nesterenko, V.F.; Meyers, M.A.

    1998-01-01

    Strain-induced chemical reactions were observed recently (Nesterenko et al) in experiments in the shear band in both Ti-Si and Nb-Si mixtures. Reactions can start in the solid state or after melting of at least one component. One of the aims is to find theoretically whether there are possible macroscopic mechanisms of mechanical intensification of the above and other chemical reactions due to plastic shear in the solid state. Continuum thermodynamical theory of structural changes with an athermal kinetics, which includes martensitic phase transformations, plastic strain-induced chemical reactions and polymorphic transformations, is developed at finite strains. The theory includes kinematics, criterion of structural change and extremum principle for determination of all unknown variable parameters for the case with neglected elastic strains. Thermodynamically consistent kinetic theory of thermally activated structural changes is suggested. The concept of the effective temperature is introduced which takes into account that temperature can vary significantly (on 1,000 K) during the chemical reactions under consideration. The theory will be applied in Part 2 of the paper for the description of chemical reactions in the shear band

  16. Transport Properties of a Kinetic Model for Chemical Reactions without Barriers

    International Nuclear Information System (INIS)

    Alves, Giselle M.; Kremer, Gilberto M.; Soares, Ana Jacinta

    2011-01-01

    A kinetic model of the Boltzmann equation for chemical reactions without energy barrier is considered here with the aim of evaluating the reaction rate and characterizing the transport coefficient of shear viscosity for the reactive system. The Chapman-Enskog solution of the Boltzmann equation is used to compute the chemical reaction effects, in a flow regime for which the reaction process is close to the final equilibrium state. Some numerical results are provided illustrating that the considered chemical reaction without energy barrier can induce an appreciable influence on the reaction rate and on the transport coefficient of shear viscosity.

  17. The redox reaction kinetics of Sinai ore for chemical looping combustion applications

    International Nuclear Information System (INIS)

    Ksepko, Ewelina; Babiński, Piotr; Nalbandian, Lori

    2017-01-01

    Highlights: • Redox reaction kinetics of Fe-Mn-rich Sinai ore was determined by TGA. • The most suitable model for reduction was D3, while R3 for oxidation. • Activation energies 35.3 and 16.70 kJ/mole were determined for reduction and oxidation. • Repetitive redox reactions favor the formation of spinel phases in Sinai ore. • Multiple redox cycles induce formation of extensive porosity of the particles. - Abstract: The objective of this work was to study the use of Sinai ore, a Fe–Mn-based ore from Egypt, as a low-cost oxygen carrier (OC) in Chemical Looping Combustion (CLC). The Sinai ore was selected because it possesses relatively high amounts of iron and manganese oxides. Furthermore, those oxides have low cost, very favorable environmental and thermodynamic properties for the CLC process. The performance of the Sinai ore as an OC in CLC was compared to that of ilmenite (Norway Tellnes mine), the most extensively studied naturally occurring Fe-based mineral. The kinetics of the reduction and oxidation reactions with the two minerals were studied using a thermogravimetric analyzer (TGA). Experiments were conducted under isothermal conditions, with multiple redox cycles, at temperatures between 750 and 950 °C. For the reduction and oxidation reactions, different concentrations of CH_4 (10–25 vol.%) and O_2 (5–20 vol.%) were applied, respectively. The kinetic parameters, such as the activation energy (E_a), pre-exponential factor (A_0), and reaction order (n), were determined for the redox reactions. Furthermore, models of the redox reactions were selected by means of a model-fitting method. For the Sinai ore, the D3 model (3-dimensional diffusion) was suitable for modeling reduction reaction kinetics. The calculated E_a was 35.3 kJ/mole, and the reaction order was determined to be approximately 0.76. The best fit for the oxidation reaction was obtained for the R3 model (shrinking core). The oxidation (regeneration) reaction E_a was equal to 16

  18. Explaining the atypical reaction profiles of heme enzymes with a novel mechanistic hypothesis and kinetic treatment.

    Directory of Open Access Journals (Sweden)

    Kelath Murali Manoj

    Full Text Available Many heme enzymes show remarkable versatility and atypical kinetics. The fungal extracellular enzyme chloroperoxidase (CPO characterizes a variety of one and two electron redox reactions in the presence of hydroperoxides. A structural counterpart, found in mammalian microsomal cytochrome P450 (CYP, uses molecular oxygen plus NADPH for the oxidative metabolism (predominantly hydroxylation of substrate in conjunction with a redox partner enzyme, cytochrome P450 reductase. In this study, we employ the two above-mentioned heme-thiolate proteins to probe the reaction kinetics and mechanism of heme enzymes. Hitherto, a substrate inhibition model based upon non-productive binding of substrate (two-site model was used to account for the inhibition of reaction at higher substrate concentrations for the CYP reaction systems. Herein, the observation of substrate inhibition is shown for both peroxide and final substrate in CPO catalyzed peroxidations. Further, analogy is drawn in the "steady state kinetics" of CPO and CYP reaction systems. New experimental observations and analyses indicate that a scheme of competing reactions (involving primary product with enzyme or other reaction components/intermediates is relevant in such complex reaction mixtures. The presence of non-selective reactive intermediate(s affords alternate reaction routes at various substrate/product concentrations, thereby leading to a lowered detectable concentration of "the product of interest" in the reaction milieu. Occam's razor favors the new hypothesis. With the new hypothesis as foundation, a new biphasic treatment to analyze the kinetics is put forth. We also introduce a key concept of "substrate concentration at maximum observed rate". The new treatment affords a more acceptable fit for observable experimental kinetic data of heme redox enzymes.

  19. Kinetic study of the reaction of chlorine atoms with hydroxyacetone in gas-phase

    Science.gov (United States)

    Stoeffler, Clara; Joly, Lilian; Durry, Georges; Cousin, Julien; Dumelié, Nicolas; Bruyant, Aurélien; Roth, Estelle; Chakir, Abdelkhaleq

    2013-12-01

    In this letter the kinetics of the reaction of hydroxyacetone CH3C(O)CH2OH with Cl atoms is investigated using the relative rate technique. Experiments are carried out in a 65 L multipass photoreactor in the temperature range of 281-350 K. A mid-infrared spectrometer based on a quantum cascade laser in external cavity emitting at 9.5 μm is used to analyze the reactants. The determined rate coefficient for the investigated reaction is (1.7 ± 0.3) × 10-11exp(381.5 ± 57.3/T). The results are presented and discussed in terms of precision and compared with those obtained previously. The impact of Cl atoms on the atmospheric life time of hydroxyacetone is also discussed. Developing analytical techniques to quantify this compound in the atmosphere. Several methods of measurement have been used including the technique of proton transfer mass spectrometry (PTR-MS) [2] and derivatization with a chemical agent such as dinitrophenylhydrazine (DNPH) [3,4] followed by GC/MS or HPLC analyses. The HA amount in the troposphere was found to be in the order of a few hundred parts per trillion by volume [4], Performing laboratory experiments in order to study the HA reactivity with atmospheric oxidants. The first study on the kinetic of the reaction between OH radicals and HA was made by Dagault et al. [5] whose work was performed at room temperature by flash photolysis-resonance fluorescence. The determined rate constant implies a lifetime of a few days for HA relative to oxidation by OH radicals. Orlando et al. performed mechanistic and kinetics studies of the reaction of HA with OH radicals and Cl atoms at room temperature using a relative method [6]. Products detection was performed using FTIR spectroscopy. Moreover, these authors studied the photolysis of HA to determine its quantum yield and UV absorption spectrum. These studies showed that HA is principally removed from the atmosphere by reaction with OH radicals. Kinetic studies of the reaction of OH radicals with HA as a

  20. Kinetics of the Reaction of CO2 with Aqueous Potassium Salt of Taurine and Glycine

    NARCIS (Netherlands)

    Kumar, P.S.; Hogendoorn, J.A.; Versteeg, G.F.; Feron, P.H.M.

    2003-01-01

    The kinetics of the reaction between CO2 and aqueous potassium salts of taurine and glycine was measured at 295 K in a stirred-cell reactor with a flat gas–liquid interface. For aqueous potassium taurate solutions, the temperature effect on the reaction kinetics was measured at 285 and 305 K. Unlike

  1. Kinetics of the reaction of CO2 with aqueous potassium salt of taurine and glycine

    NARCIS (Netherlands)

    Kumar Paramasivam Senthil, P.S.; Hogendoorn, Kees; Versteeg, Geert; Feron, P.H.M.

    2003-01-01

    The kinetics of the reaction between CO2 and aqueous potassium salts of taurine and glycine was measured at 295 K in a stirred-cell reactor with a flat gas-liquid interface. For aqueous potassium taurate solutions, the temperature effect on the reaction kinetics was measured at 285 and 305 K. Unlike

  2. The kinetics of the reduction reaction of plutonium(IV) with N,N-dimethylhydroxylamine

    International Nuclear Information System (INIS)

    Yanxin Chen; Honbing Tang; Jinping Liu; Hui He

    2011-01-01

    The kinetics of reduction reactions between N,N-dimethylhydroxylamine (DMHAN) and plutonium(IV) in nitric acid solution have been studied spectrophotometrically. The kinetic equation of the reaction is determined to be -d[Pu(IV)]/dt = k 0 [Pu(IV)][DMHAN] 1.18 /[H + ] 2.22 at the beginning, where, the rate constant of the reaction (k 0 ) is 10.5 ± 1.8(mol/L) 1.04 s -1 at 14.5 deg C. By regressing of the time-concentration curve of the reaction, The complete rate equation is calculated as -d[Pu(IV)] / dt = k[Pu(IV)] 2 [DMHAN] 1.18 /[H + ] 2.22 / 8.12[Pu(III)]+95.9[Pu(IV)] with the reaction constant k about 1,000(mol/L) 1.04 s -1 at 14.5 deg C and an ionic strength (μ) of 4.0 mol/L. (author)

  3. Reaction kinetics for preparation of silica film with Stoeber method

    International Nuclear Information System (INIS)

    Shang Mengying; Jiang Xiaodong; Liu Miao; Luo Xuan; Tang Yongjian; Cao Linhong

    2013-01-01

    A new formula was proposed to investigate the relationship between reaction time and tetraethylorthosilicate (TEOS) conversion rate for preparation of silica sol with Stöber method, by studying the reaction kinetics of TEOS hydrolytic process. An appropriate conversion rate was then determined and used to calculate the theoretical optimal reaction time. Meanwhile, silica sols were prepared by sol-gel process using TEOS as precursor and ammonia as catalyst. It was found that the reaction time decreases with an increasing amount of ammonia and water. The values of experimental optimal reaction time were obtained, and agree with the theoretical results (the errors are within 5%), which shows good applicability of our formula. (authors)

  4. Conductometric Studies Of Kinetics Of Ionic Reaction Between Ag And Cl- In Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Md. Rezwan Miah

    2017-01-01

    Full Text Available In the present report conductometric studies on the kinetic of formation of AgCl by ionic reaction between Ag and Clamp61485 in aqueous solution have been presented. The order of the mentioned reaction was determined by a new conductometric approach using half-life method. The obtained result showed that the reaction follows a second-order kinetics. The second-order rate constant of the reaction was obtained conductometrically using different initial concentrations of the reactants in the range of 2.5-5.0 mM. The average value of the rate constant was obtained as 20.648 L molamp614851 samp614851 at 25 amp61616C.

  5. Thermo-Kinetic Investigation of Comparative Ligand Effect on Cysteine Iron Redox Reaction

    Directory of Open Access Journals (Sweden)

    Masood Ahmad Rizvi

    2015-03-01

    Full Text Available Transition metal ions in their free state bring unwanted biological oxidations generating oxidative stress. The ligand modulated redox potential can be indispensable in prevention of such oxidative stress by blocking the redundant bio-redox reactions. In this study we investigated the comparative ligand effect on the thermo-kinetic aspects of biologically important cysteine iron (III redox reaction using spectrophotometric and potentiometric methods. The results were corroborated with the complexation effect on redox potential of iron(III-iron(II redox couple. The selected ligands were found to increase the rate of cysteine iron (III redox reaction in proportion to their stability of iron (II complex (EDTA < terpy < bipy < phen. A kinetic profile and the catalytic role of copper (II ions by means of redox shuttle mechanism for the cysteine iron (III redox reaction in presence of 1,10-phenanthroline (phen ligand is also reported.

  6. Kinetics and optimization on discoloration of dyeing wastewater by schorl-catalyzed fenton-like reaction

    Directory of Open Access Journals (Sweden)

    Xu Huan-Yan

    2014-01-01

    Full Text Available Kinetics and optimization on the discoloration of an active commercial dye, Argazol Blue BFBR (ABB by heterogeneous Fenton-like reaction catalyzed by natural schorl were investigated in this study. Kinetic investigations revealed that the first-order kinetic model was more favorable to describe the discoloration of ABB at different reaction conditions than the second-order and Behnajady-Modirshahla-Ghanbery models. The relationship between the reaction rate constant k and reaction temperature T followed the Arrhenius equation, with the apparent activation energy Ea of 51.31kJ•mol-1. The central composite design under the response surface methodology was employed for the experimental design and optimization of the ABB discoloration process. The significance of a second order polynomial model for predicting the optimal values of ABB discoloration was evaluated by the analysis of variance and 3D response surface plots for the interactions between two variables were constructed. Then, the optimum conditions were determined.

  7. SABIO-RK: an updated resource for manually curated biochemical reaction kinetics

    Science.gov (United States)

    Rey, Maja; Weidemann, Andreas; Kania, Renate; Müller, Wolfgang

    2018-01-01

    Abstract SABIO-RK (http://sabiork.h-its.org/) is a manually curated database containing data about biochemical reactions and their reaction kinetics. The data are primarily extracted from scientific literature and stored in a relational database. The content comprises both naturally occurring and alternatively measured biochemical reactions and is not restricted to any organism class. The data are made available to the public by a web-based search interface and by web services for programmatic access. In this update we describe major improvements and extensions of SABIO-RK since our last publication in the database issue of Nucleic Acid Research (2012). (i) The website has been completely revised and (ii) allows now also free text search for kinetics data. (iii) Additional interlinkages with other databases in our field have been established; this enables users to gain directly comprehensive knowledge about the properties of enzymes and kinetics beyond SABIO-RK. (iv) Vice versa, direct access to SABIO-RK data has been implemented in several systems biology tools and workflows. (v) On request of our experimental users, the data can be exported now additionally in spreadsheet formats. (vi) The newly established SABIO-RK Curation Service allows to respond to specific data requirements. PMID:29092055

  8. Energetics and kinetics of ferrocyanide and nitrate/nitrite reactions

    International Nuclear Information System (INIS)

    Scheele, R.D.; Burger, L.L.; Sell, R.L.

    1994-01-01

    During the 1950's, radiocesium scavenging at the Hanford site resulted in radioactive waste sludges containing ferrocyanide, nitrate, and nitrite. These waters are a concern since certain mixtures of ferrocyanide and nitrate and/or nitrite are known to explode when heated. The authors have used differential scanning calorimetry, thermogravimetric analysis, isothermal calorimetry and gravimetry, and accelerating rate calorimetry to measure the thermal behavior, the reaction enthalpies, and selected kinetic parameters for reactions between sodium nickel ferrocyanide, the suspected ferrocyanide form in Hanford wastes, and nitrate and/or nitrite. These studies indicate that the oxidation proceeds via multiple steps, the initial reaction begins near 200 degrees C, the initial step has a high activation energy (>200 kJ/mole-K), succeeding reaction steps have activation energies ranging from 90 to 160 kJ/mole-K, and that the oxidation yields about 50% of the theoretical heat of reaction for the most energetic reaction

  9. Investigation of Coal-biomass Catalytic Gasification using Experiments, Reaction Kinetics and Computational Fluid Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Battaglia, Francine [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Agblevor, Foster [Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Klein, Michael [Univ. of Delaware, Newark, DE (United States); Sheikhi, Reza [Northeastern Univ., Boston, MA (United States)

    2015-12-31

    A collaborative effort involving experiments, kinetic modeling, and computational fluid dynamics (CFD) was used to understand co-gasification of coal-biomass mixtures. The overall goal of the work was to determine the key reactive properties for coal-biomass mixed fuels. Sub-bituminous coal was mixed with biomass feedstocks to determine the fluidization and gasification characteristics of hybrid poplar wood, switchgrass and corn stover. It was found that corn stover and poplar wood were the best feedstocks to use with coal. The novel approach of this project was the use of a red mud catalyst to improve gasification and lower gasification temperatures. An important results was the reduction of agglomeration of the biomass using the catalyst. An outcome of this work was the characterization of the chemical kinetics and reaction mechanisms of the co-gasification fuels, and the development of a set of models that can be integrated into other modeling environments. The multiphase flow code, MFIX, was used to simulate and predict the hydrodynamics and co-gasification, and results were validated with the experiments. The reaction kinetics modeling was used to develop a smaller set of reactions for tractable CFD calculations that represented the experiments. Finally, an efficient tool was developed, MCHARS, and coupled with MFIX to efficiently simulate the complex reaction kinetics.

  10. Accurate label-free reaction kinetics determination using initial rate heat measurements

    Science.gov (United States)

    Ebrahimi, Kourosh Honarmand; Hagedoorn, Peter-Leon; Jacobs, Denise; Hagen, Wilfred R.

    2015-01-01

    Accurate label-free methods or assays to obtain the initial reaction rates have significant importance in fundamental studies of enzymes and in application-oriented high throughput screening of enzyme activity. Here we introduce a label-free approach for obtaining initial rates of enzyme activity from heat measurements, which we name initial rate calorimetry (IrCal). This approach is based on our new finding that the data recorded by isothermal titration calorimetry for the early stages of a reaction, which have been widely ignored, are correlated to the initial rates. Application of the IrCal approach to various enzymes led to accurate enzyme kinetics parameters as compared to spectroscopic methods and enabled enzyme kinetic studies with natural substrate, e.g. proteases with protein substrates. Because heat is a label-free property of almost all reactions, the IrCal approach holds promise in fundamental studies of various enzymes and in use of calorimetry for high throughput screening of enzyme activity. PMID:26574737

  11. Nonequilibrium transition and pattern formation in a linear reaction-diffusion system with self-regulated kinetics

    Science.gov (United States)

    Paul, Shibashis; Ghosh, Shyamolina; Ray, Deb Shankar

    2018-02-01

    We consider a reaction-diffusion system with linear, stochastic activator-inhibitor kinetics where the time evolution of concentration of a species at any spatial location depends on the relative average concentration of its neighbors. This self-regulating nature of kinetics brings in spatial correlation between the activator and the inhibitor. An interplay of this correlation in kinetics and disparity of diffusivities of the two species leads to symmetry breaking non-equilibrium transition resulting in stationary pattern formation. The role of initial noise strength and the linear reaction terms has been analyzed for pattern selection.

  12. A new fundamental hydrogen defect in alkali halides

    International Nuclear Information System (INIS)

    Morato, S.P.; Luety, F.

    1978-01-01

    Atom hydrogen in neutral (H 0 ) and negative (H - ) form on substitutional and interstitial lattice sites gives rise to well characterized model defects in alkali-halides (U,U 1 ,U 2 ,U 3 centers), which have been extensively investigated in the past. When studying the photo-decomposition of OH - defects, a new configuration of atomic charged hidrogen was discovered, which can be produced in large quantities in the crystal and is apparently not connected to any other impurity. This new hidrogen defect does not show any pronounced electronic absorption, but displays a single sharp local mode band (at 1114cm -1 in KCl) with a perfect isotope shift. The defect can be produced by various UV or X-ray techniques in crystais doped with OH - , Sh - or H - defects. A detailed study of its formation kinetics at low temperature shows that it is primarily formed by the reaction of a mobile CI 2 - crowdion (H-center) with hidrogen defects [pt

  13. Reactions of plutonium and uranium with water: Kinetics and potential hazards

    International Nuclear Information System (INIS)

    Haschke, J.M.

    1995-12-01

    The chemistry and kinetics of reactions between water and the metals and hydrides of plutonium and uranium are described in an effort to consolidate information for assessing potential hazards associated with handling and storage. New experimental results and data from literature sources are presented. Kinetic dependencies on pH, salt concentration, temperature and other parameters are reviewed. Corrosion reactions of the metals in near-neutral solutions produce a fine hydridic powder plus hydrogen. The corrosion rate for plutonium in sea water is a thousand-fold faster than for the metal in distilled water and more than a thousand-fold faster than for uranium in sea water. Reaction rates for immersed hydrides of plutonium and uranium are comparable and slower than the corrosion rates for the respective metals. However, uranium trihydride is reported to react violently if a quantity greater than twenty-five grams is rapidly immersed in water. The possibility of a similar autothermic reaction for large quantities of plutonium hydride cannot be excluded. In addition to producing hydrogen, corrosion reactions convert the massive metals into material forms that are readily suspended in water and that are aerosolizable and potentially pyrophoric when dry. Potential hazards associated with criticality, environmental dispersal, spontaneous ignition and explosive gas mixtures are outlined

  14. 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

  15. Coarse-grained molecular dynamics modeling of the kinetics of lamellar block copolymer defect annealing

    Science.gov (United States)

    Peters, Andrew J.; Lawson, Richard A.; Nation, Benjamin D.; Ludovice, Peter J.; Henderson, Clifford L.

    2016-01-01

    State-of-the-art block copolymer (BCP)-directed self-assembly (DSA) methods still yield defect densities orders of magnitude higher than is necessary in semiconductor fabrication despite free-energy calculations that suggest equilibrium defect densities are much lower than is necessary for economic fabrication. This disparity suggests that the main problem may lie in the kinetics of defect removal. This work uses a coarse-grained model to study the rates, pathways, and dependencies of healing a common defect to give insight into the fundamental processes that control defect healing and give guidance on optimal process conditions for BCP-DSA. It is found that bulk simulations yield an exponential drop in defect heal rate above χN˜30. Thin films show no change in rate associated with the energy barrier below χN˜50, significantly higher than the χN values found previously for self-consistent field theory studies that neglect fluctuations. Above χN˜50, the simulations show an increase in energy barrier scaling with 1/2 to 1/3 of the bulk systems. This is because thin films always begin healing at the free interface or the BCP-underlayer interface, where the increased A-B contact area associated with the transition state is minimized, while the infinitely thick films cannot begin healing at an interface.

  16. Kinetics and mechanisms of reactions involving small aromatic reactive intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Lin, M.C. [Emory Univ., Atlanta, GA (United States)

    1993-12-01

    Small aromatic radicals such as C{sub 6}H{sub 5}, C{sub 6}H{sub 5}O and C{sub 6}H{sub 4} are key prototype species of their homologs. C{sub 6}H{sub 5} and its oxidation product, C{sub 6}H{sub 5}O are believed to be important intermediates which play a pivotal role in hydrocarbon combustion, particularly with regard to soot formation. Despite their fundamental importance, experimental data on the reaction mechanisms and reactivities of these species are very limited. For C{sub 6}H{sub 5}, most kinetic data except its reactions with NO and NO{sub 2}, were obtained by relative rate measurements. For C{sub 6}H{sub 5}O, the authors have earlier measured its fragmentation reaction producing C{sub 5}H{sub 5} + CO in shock waves. For C{sub 6}H{sub 4}, the only rate constant measured in the gas phase is its recombination rate at room temperature. The authors have proposed to investigate systematically the kinetics and mechanisms of this important class of molecules using two parallel laser diagnostic techniques--laser resonance absorption (LRA) and resonance enhanced multiphoton ionization mass spectrometry (REMPI/MS). In the past two years, study has been focused on the development of a new multipass adsorption technique--the {open_quotes}cavity-ring-down{close_quotes} technique for kinetic applications. The preliminary results of this study appear to be quite good and the sensitivity of the technique is at least comparable to that of the laser-induced fluorescence method.

  17. Thermodynamic criteria for estimating the kinetic parameters of catalytic reactions

    Science.gov (United States)

    Mitrichev, I. I.; Zhensa, A. V.; Kol'tsova, E. M.

    2017-01-01

    Kinetic parameters are estimated using two criteria in addition to the traditional criterion that considers the consistency between experimental and modeled conversion data: thermodynamic consistency and the consistency with entropy production (i.e., the absolute rate of the change in entropy due to exchange with the environment is consistent with the rate of entropy production in the steady state). A special procedure is developed and executed on a computer to achieve the thermodynamic consistency of a set of kinetic parameters with respect to both the standard entropy of a reaction and the standard enthalpy of a reaction. A problem of multi-criterion optimization, reduced to a single-criterion problem by summing weighted values of the three criteria listed above, is solved. Using the reaction of NO reduction with CO on a platinum catalyst as an example, it is shown that the set of parameters proposed by D.B. Mantri and P. Aghalayam gives much worse agreement with experimental values than the set obtained on the basis of three criteria: the sum of the squares of deviations for conversion, the thermodynamic consistency, and the consistency with entropy production.

  18. KEMOD: A mixed chemical kinetic and equilibrium model of aqueous and solid phase geochemical reactions

    International Nuclear Information System (INIS)

    Yeh, G.T.; Iskra, G.A.

    1995-01-01

    This report presents the development of a mixed chemical Kinetic and Equilibrium MODel in which every chemical species can be treated either as a equilibrium-controlled or as a kinetically controlled reaction. The reaction processes include aqueous complexation, adsorption/desorption, ion exchange, precipitation/dissolution, oxidation/reduction, and acid/base reactions. Further development and modification of KEMOD can be made in: (1) inclusion of species switching solution algorithms, (2) incorporation of the effect of temperature and pressure on equilibrium and rate constants, and (3) extension to high ionic strength

  19. Variable elimination in chemical reaction networks with mass-action kinetics

    DEFF Research Database (Denmark)

    Feliu, Elisenda; Wiuf, C.

    2012-01-01

    We consider chemical reaction networks taken with mass-action kinetics. The steady states of such a system are solutions to a system of polynomial equations. Even for small systems the task of finding the solutions is daunting. We develop an algebraic framework and procedure for linear elimination...

  20. Kinetics based reaction optimization of enzyme catalysed reduction of formaldehyde to methanol with synchronous cofactor regeneration

    DEFF Research Database (Denmark)

    Marpani, Fauziah Binti; Sárossy, Zsuzsa; Pinelo, Manuel

    2017-01-01

    regeneration of the reducing equivalents during reaction is required. Herein, we report the optimization of the enzymatic conversion of formaldehyde (CHOH) to CH3 OH by alcohol dehydrogenase, the final step of the enzymatic redox reaction of CO2 to CH3 OH, with kinetically synchronous enzymatic cofactor...... regeneration using either glucose dehydrogenase (System I) or xylose dehydrogenase (System II). A mathematical model of the enzyme kinetics was employed to identify the best reaction set-up for attaining optimal cofactor recycling rate and enzyme utilization efficiency. Targeted process optimization...... experiments were conducted to verify the kinetically modelled results. Repetitive reaction cycles were shown to enhance the yield of CH3 OH, increase the total turnover number (TTN) and the biocatalytic productivity rate (BPR) value for both system I and II whilst minimizing the exposure of the enzymes...

  1. Simulation of the accumulation kinetics for radiation point defects in a metals with impurity

    International Nuclear Information System (INIS)

    Iskakov, B.M.; Nurova, A.B.

    2001-01-01

    In the work a kinetics of vacancies (V) and interstitial atoms (IA) accumulation for cases when the V and IA are recombining with each other, absorbing by drain and capturing by impurity atoms has been simulated. The differential equations system numerical solution was carried out by the Runge-Kutta method. The dynamical equilibrium time achievement for the point radiation defects accumulation process in the metal with impurity is considered

  2. Reaction network modelling for kinetic parameters of pyrolytic reactions of CHON extractants in nuclear fuel processing waste management. Contributed Paper IT-07

    International Nuclear Information System (INIS)

    Gaikar, Vilas G.; Thaore, Vaishali

    2014-01-01

    The recovery and purification of plutonium (Pu) from uranium (U) and of U from Thorium (Th) in spent nuclear fuel reprocessing is accomplished by processes that employ organophosphorous compounds as extractants.The main objective of the present work was to develop a suitable kinetic model and to determine the kinetic parameters of the set of reactions involved in the pyrolysis of amides by fitting the experimental data in the reaction network model. The experimental data and analysis are expected to be useful in the steam pyrolysis of amide waste in fuel reprocessing in the nuclear industry. The basic approach was to understand the reaction mechanism of the steam pyrolysis of amides and then to estimate the reaction rate constants for the generation and consumption of different species by solving the model equations, allowing for the determination of important species in the reaction network

  3. Coarse-grained molecular dynamics modeling of the kinetics of lamellar BCP defect annealing

    Science.gov (United States)

    Peters, Andrew J.; Lawson, Richard A.; Nation, Benjamin D.; Ludovice, Peter J.; Henderson, Clifford L.

    2015-03-01

    Directed self-assembly of block copolymers (BCPs) is a process that has received great interest in the field of nanomanufacturing in the past decade, and great strides towards forming high quality aligned patterns have been made. But state of the art methods still yield defectivities orders of magnitude higher than is necessary in semi-conductor fabrication even though free energy calculations suggest that equilibrium defectivities are much lower than is necessary for economic semi-conductor fabrication. This disparity suggests that the main problem may lie in the kinetics of defect removal. This work uses a coarse-grained model to study the rates, pathways, and dependencies of healing a common defect to give insight into the fundamental processes that control defect healing and give guidance on optimal process conditions for BCP-DSA. It is found that infinitely thick films yield an exponential drop in defect heal rate above χN ~ 30. Below χN ~ 30, the rate of transport was similar to the rate at which the transition state was reached so that the overall rate changed only slightly. The energy barrier in periodic simulations increased with 0.31 χN on average. Thin film simulations show no change in rate associated with the energy barrier below χN ~ 50, and then show an increase in energy barrier scaling with 0.16χN. Thin film simulations always begin to heal at either the free interface or the BCP-underlayer interface where the increased A-B contact area associated with the transition state will be minimized, while the infinitely thick films must start healing in the bulk where the A-B contact area is increased. It is also found that cooperative chain movement is required for the defect to start healing.

  4. Kinetic study on bonding reaction of gelatin with CdS nanopaticles by UV-visible spectroscopy.

    Science.gov (United States)

    Tang, Shihua; Wang, Baiyang; Li, Youqun

    2015-04-15

    The chemical kinetics on gelatin-CdS direct conjugates has been systematically investigated as a function of different temperature and reactant concentration (i.e. Cd(2+), S(2-) and gelatin) by UV-visible spectroscopy, for the first time. The nonlinear fitting and the differential method were used to calculate the initial rate based on the absorbance-time data. A double logarithmic linear equation for calculating the rate constant (k) and the reaction order (n) was introduced. The reaction kinetic parameters (n, k, Ea, and Z) and activation thermodynamic parameters (ΔG(≠), ΔH(≠), and ΔS(≠)) were obtained from variable temperature kinetic studies. The overall rate equation allowing evaluation of conditions that provide required reaction rate could be expressed as: r = 1.11 × 10(8) exp(-4971/T)[Cd(2+)][gelatin](0.6)[S(2-)](0.6) (M/S) The calculated values of the reaction rate are well coincide with the experimental results. A suitable kinetic model is also proposed. This work will provide guidance for the rational design of gelatin-directed syntheses of metal sulfide materials, and help to understand the biological effects of nanoparticles at the molecular level. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Penicillin Hydrolysis: A Kinetic Study of a Multistep, Multiproduct Reaction.

    Science.gov (United States)

    McCarrick, Thomas A.; McLafferty, Fred W.

    1984-01-01

    Background, procedures used, and typical results are provided for an experiment in which students carry out the necessary measurements on the acid-catalysis of penicillin in two hours. By applying kinetic theory to the data obtained, the reaction pathways for the hydrolysis of potassium benzyl penicillin are elucidated. (JN)

  6. Kinetics of barium sulphate reaction crystallization in crystallizers with internal circulation

    Directory of Open Access Journals (Sweden)

    J. Koralewska

    2008-06-01

    Full Text Available Kinetic calculation results describing the observed nucleation and growth rates of barium sulphate crystals precipitated in an integrated reaction-crystallization process in a barium sulphate-ammonium chloride-water system are presented and analyzed. The scope of experiments included two continuous model DTM-type crystallizers (Draft Tube Magma with internal circulation of the suspension forced by a liquid jet-pump device responsible for stable and intensive enough ascending/descending flow of BaSO4 crystal magma in a mixing chamber. For comparison purposes the experimental data corresponding to a continuous DT (Draft Tube crystallizer with propeller agitator are presented and discussed. The various types of laboratory crystallizers used were fed with concentrated water solution of barium chloride (of 10 or 24 mass % and - in a stoichiometric proportion - crystalline ammonium sulphate, assuming isothermal (348 K and hydrodynamic (average residence time of suspension in a crystallizer: 900 s process conditions. The observed nucleation and growth rates of barium sulphate crystals were estimated on the basis of crystal size distributions (CSDs using convenient calculation scheme derived for an MSMPR (Mixed Suspension Mixed Product Removal model approach. Considering the experimental population density distribution courses, a size-dependent growth (SDG phenomenon was taken into account in the kinetic calculations. Five SDG kinetic models recommended in the accessible literature were used for kinetic parameter values estimation. It was proved statistically, that Rojkowski’s two SDG models (hyperbolic and exponential best suit for our own experimental data description. The experimental data presented can be practically applied for improving the constructions of liquid jet-pump DTM crystallizers recommended for reaction crystallization of sparingly soluble inorganic salts (especially for high concentrations of reaction substrates in the modern

  7. Defect kinetics in novel detector materials

    CERN Document Server

    MacEvoy, B C

    2000-01-01

    Silicon particle detectors will be used extensively in experiments at the CERN Large Hadron Collider, where unprecedented particle fluences will cause significant atomic displacement damage. We present a model of the evolution of defect concentrations and consequent electrical behaviour in "novel" detector materials with various oxygen and carbon impurity concentrations. The divacancy-oxygen (V/sub 2/O) defect is identified as the cause of changes in device characteristics during /sup 60/Co gamma irradiation. In the case of hadron irradiation changes in detector doping concentration (N/sub eff/) are dominated by cluster defects, in particular the divacancy (V/sub 2/), which exchange charge directly via a non-Shockley-Read- Hall mechanism. The V/sub 2/O defect also contributes to Ne/sub eff/. This defect is more copiously produced during 24 GeV/c proton irradiation than during 1 MeV neutron irradiation on account of the higher vacancy introduction rate, hence the radiation hardness of materials is more sensiti...

  8. Heterogeneous reaction mechanisms and kinetics relevant to the CVD of semiconductor materials

    Energy Technology Data Exchange (ETDEWEB)

    Creighton, J.R.; Coltrin, M.E.

    1994-03-01

    This report documents the state of the art in experimental and theoretical techniques for determining reaction mechanisms and chemical kinetics of heterogeneous reactions relevant to the chemical vapor deposition of semiconductor materials. It summarizes the most common ultra-high vacuum experimental techniques that are used and the types of rate information available from each. Several case studies of specific chemical systems relevant to the microelectronics industry are described. Theoretical methods for calculating heterogeneous reaction rate constants are also summarized.

  9. Determining Li+-Coupled Redox Targeting Reaction Kinetics of Battery Materials with Scanning Electrochemical Microscopy.

    Science.gov (United States)

    Yan, Ruiting; Ghilane, Jalal; Phuah, Kia Chai; Pham Truong, Thuan Nguyen; Adams, Stefan; Randriamahazaka, Hyacinthe; Wang, Qing

    2018-02-01

    The redox targeting reaction of Li + -storage materials with redox mediators is the key process in redox flow lithium batteries, a promising technology for next-generation large-scale energy storage. The kinetics of the Li + -coupled heterogeneous charge transfer between the energy storage material and redox mediator dictates the performance of the device, while as a new type of charge transfer process it has been rarely studied. Here, scanning electrochemical microscopy (SECM) was employed for the first time to determine the interfacial charge transfer kinetics of LiFePO 4 /FePO 4 upon delithiation and lithiation by a pair of redox shuttle molecules FcBr 2 + and Fc. The effective rate constant k eff was determined to be around 3.70-6.57 × 10 -3 cm/s for the two-way pseudo-first-order reactions, which feature a linear dependence on the composition of LiFePO 4 , validating the kinetic process of interfacial charge transfer rather than bulk solid diffusion. In addition, in conjunction with chronoamperometry measurement, the SECM study disproves the conventional "shrinking-core" model for the delithiation of LiFePO 4 and presents an intriguing way of probing the phase boundary propagations induced by interfacial redox reactions. This study demonstrates a reliable method for the kinetics of redox targeting reactions, and the results provide useful guidance for the optimization of redox targeting systems for large-scale energy storage.

  10. Study of kinetics of reaction of lithium deuteride powder with O2, CO2 and water vapor

    International Nuclear Information System (INIS)

    Li Gan; Lu Guangda; Jing Wenyong; Qin Cheng

    2004-01-01

    The kinetics of reaction of lithium deuteride powder with O 2 , CO 2 and water vapor is studied. The experimental results show that lithium deuteride reacts with O 2 and CO 2 at very small reaction rate but with water vapor at comparatively larger rate at room temperature (≅28 degree C). The reaction process with water vapor could be described using the unreacted shrinking core model. The second-order kinetics is appropriate for the chemical reaction on the surface of lithium deuteride and reaction rate constant is 0.281 kPa -1 ·min -1

  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. KINETIC MODELS STUDY OF HYDRODESULPHURIZATION VACUUM DISTILLATE REACTION

    Directory of Open Access Journals (Sweden)

    AbdulMunem A. Karim

    2013-05-01

    Full Text Available    This study deals with  kinetics of hydrodesulphurization (HDS reaction of vacuum gas oil (611-833 K which was distillated from Kirkuk crude oil and which was obtained by blending the fractions, light vacuum gas oil (611 - 650 K, medium vacuum gas oil (650-690 K, heavy vacuum gas oil (690-727 K and very heavy vacuum gas oil (727-833 K.   The vacuum gas oil was hydrotreated on a commercial cobalt-molybdenum alumina catalyst presulfied at specified conditions in a laboratory trickle bed reactor. The reaction temperature range (583-643 K,liquid hourly space velocity range (1.5-3.75 h-1 and hydrogen pressure was kept constant at 3.5 MPa with hydrogen to oil ratio about 250 lt/lt.           The conversion results for desulphurization reaction appeared to obey the second order reaction. According to this model, the rate constants for desulphurization reaction were determined. Finally, the apparent activation energy (Ea, enthalpy of activation ( H* and entropy ( S* were calculated based on the values of rate constant (k2 and were equal 80.3792 KJ/mole, 75.2974 KJ/mole and 197.493 J/mole, respectively.

  13. Kinetic Studies of Oxidative Coupling of Methane Reaction on Model Catalysts

    KAUST Repository

    Khan, Abdulaziz M.

    2016-01-01

    the process to be commercialized despite the fact that great number of attempts to prepare catalysts were conducted so that it can be economically viable. Due to these limitations, understanding the mechanism and kinetics of the reaction can be utilized

  14. Kinetics of the hydrogen production reaction in a copper-chlorine water splitting plant

    International Nuclear Information System (INIS)

    Zamfirescu, C.; Naterer, G.F.; Dincer, I.

    2009-01-01

    The exothermic reaction of HCl with particulate Cu occurs during hydrogen production step in the thermochemical copper-chlorine (Cu-Cl) water splitting cycle. In this paper, this chemical reaction is modeled kinetically, and a parametric study is performed to determine the influences of particle size, temperature and molar ratios on the reaction kinetics. It is determined that the residence time of copper particles varies between 10 and 100 s, depending on the operating conditions. The hydrogen conversion at equilibrium varies between 55 and 85%, depending on the reaction temperature. The heat flux at the particle surface, caused by the exothermic enthalpy of reaction, reaches about 3,000 W/m 2 when the particle shrinks to 0.1% from its initial size. A numerical algorithm is developed to solve the moving boundary Stefan problem with a chemical reaction. It predicts the shrinking of copper particles based on the hypothesis that the chemical reaction and heat transfer are decoupled. The model allows for estimation of the temperature of the copper particle, assumed spherical, in the radial direction. The maximum temperature at the interface is higher than the melting point of CuCl by 10-50 o C, depending on the assumed operating conditions. (author)

  15. Configuration of a pulse radiolysis system for the study of gas-phase reactions and kinetic investigations of the reactions of hydroxyl radicals with methyl and ethyl radicals

    International Nuclear Information System (INIS)

    Fagerstroem, K.

    1993-01-01

    The work that is presented in this thesis deals with the assembling and testing of a pulse radiolysis system for kinetic studies of gas-phase reactions as well as with the kinetics of the gas-phase reactions of hydroxyl radicals with methyl and ethyl radicals. These radicals are very important as these are formed at an early stage in hydrocarbon combustion processes. The two studied reactions are key reactions in those processes. (6 refs., 4 figs., 2 tabs.)

  16. Modelling and experimental evaluation of reaction kinetics in reactive extraction for chiral separation of amines, amino acids and amino-alcohols

    NARCIS (Netherlands)

    Steensma, M.; Kuipers, N.J.M.; de Haan, A.B.; Kwant, Gerard

    2007-01-01

    This paper reports on determination of the intrinsic reaction kinetics in reactive extraction of chiral compounds. It is important to know the mass transfer rates and reaction kinetics separately for a reliable scale-up. A kinetic model is developed to interpret the experimental data from the

  17. Hydrolysis of Surfactants Containing Ester Bonds: Modulation of Reaction Kinetics and Important Aspects of Surfactant Self-Assembly

    Science.gov (United States)

    Lundberg, Dan; Stjerndahl, Maria

    2011-01-01

    The effects of self-assembly on the hydrolysis kinetics of surfactants that contain ester bonds are discussed. A number of examples on how reaction rates and apparent reaction orders can be modulated by changes in the conditions, including an instance of apparent zero-order kinetics, are presented. Furthermore, it is shown that the examples on…

  18. A study of redox kinetic in silicate melt; Etude cinetique des reactions d'oxydoreduction dans les silicates

    Energy Technology Data Exchange (ETDEWEB)

    Magnien, V

    2005-12-15

    The aim of this thesis is to understand better iron redox reactions and mechanisms in silicate glasses and melts. Particular interest has been paid to the influence of temperature and chemical composition. For this purpose, the influence of alkali element content, iron content and network formers on the kinetics of redox reactions has been determined through XANES and Raman spectroscopy experiments performed either near the glass transition or above the liquidus temperature. As a complement, electrical conductivity and RBS spectroscopy experiments have been made to characterize the diffusivity of the species that transport electrical charges and the reaction morphology, respectively. Temperature and composition variations can induce changes in the dominating redox mechanism. At a given temperature, the parameters that exert the strongest influence on redox mechanisms are the presence or lack of divalent cations and the existing decoupling between the mobility of network former and modifier elements. Near Tg, the diffusion of divalent cations, when present in the melt, controls the kinetics of iron redox reactions along with a flux of electron holes. Composition, through the degree of polymerization and the silicate network structure, influences the kinetics and the nature of the involved cations, but not the mechanisms of the reaction. Without alkaline earth elements, the kinetics of redox reactions are controlled by the diffusion of oxygen species. With increasing temperatures, the diffusivities of all ionic species tend to become similar. The decoupling between ionic fluxes then is reduced so that several mechanisms become kinetically equivalent and can thus coexist. (author)

  19. Investigation of the kinetics and mechanism of the glycerol chlorination reaction using gas chromatography–mass spectrometry

    Directory of Open Access Journals (Sweden)

    JUN WANG

    2010-01-01

    Full Text Available As a primary by-product in biodiesel production, glycerol can be used to prepare an important fine chemical, epichlorohydrin, by the glycerol chlorination reaction. Although this process has been applied in industrial production, unfortunately, less attention has been paid to the analysis and separation of the compounds in the glycerol chlorination products. In this study, a convenient and accurate method to determine the products in glycerol chlorination reaction was established and based on the results the kinetic mechanism of the reaction was investigated. The structure of main products, including 1,3--dichloropropan-2-ol, 2,3-dichloropropan-1-ol, 3-chloro-1,2-propanediol, 2-chloro-1,3-propanediol and glycerol was ascertained by gas chromatography–mass spectrometry and the isomers of the products were distinguished. Apidic acid was considered as the best catalyst because of its excellent catalytic effect and high boiling point. The mechanism of the glycerol chlorination reaction was proposed and a new kinetic model was developed. Kinetic equations of the process in the experimental range were obtained by data fitting and the activation energies of each tandem reaction were 30.7, 41.8, 29.4 and 49.5 kJ mol-1, respectively. This study revealed the process and mechanism of the kinetics and provides the theoretical basis for engineering problems.

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

    Science.gov (United States)

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

    2014-10-05

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

  1. Characterization of excited-state reactions with instant spectra of fluorescence kinetics

    International Nuclear Information System (INIS)

    Tomin, Vladimir I.; Ushakou, Dzmitryi V.

    2015-01-01

    Comprehensible knowledge of the excited-state proton transfer processes in organic compounds is overwhelmingly important not only for physics, but also chemistry and Life Sciences, since they play a key role in main processes of photosynthesis and functioning of biological organisms. Moreover compounds with Excited-State Intramolecular Proton Transfer (ESIPT) are in the focus of the interest of scientists throughout the world, because dual fluorescence spectra of such objects corresponding to two forms of molecular structure (normal and photoproduct) are very sensitive to characteristics of molecular microenvironment. This property allows to use such substances as fluorescent probes for diverse applications in chemistry and Life Sciences. But at the same time studying of proton transfer processes is not simple, because this process is characterized by extremely fast times (on picoseconds time scale and less order) and very often contribution of reverse reactions is essentially complicates an interpretation of observed properties of dual fluorescence. Hence, understanding of a role of reversible reactions is crucial for a comprehensive description of all processes accompanying excited state reactions. We discuss new approach for treatment ESIPT reaction on the basis of experimentally measured instant spectra of dual fluorescence and temporal behavior of ratiometric signal of normal to tautomer form intensities. Simple analytical expressions show in transparent way how to distinguish a degree of reverse reaction contribution to ratiometric signal. A validation of the approach under consideration is fulfilled with two different flavonols – 3-hydroxyflavone and 4′-(Dimethylamino)-3-hydroxyflavone – representing two extreme cases in affecting reversible reaction on dual emission. A comparing of new approach and traditional method when we analyze kinetics of separate the N* and T* fluorescence bands decays, has been carried out. - Highlights: • The excited

  2. Characterization of excited-state reactions with instant spectra of fluorescence kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Tomin, Vladimir I., E-mail: tomin@apsl.edu.pl; Ushakou, Dzmitryi V.

    2015-10-15

    Comprehensible knowledge of the excited-state proton transfer processes in organic compounds is overwhelmingly important not only for physics, but also chemistry and Life Sciences, since they play a key role in main processes of photosynthesis and functioning of biological organisms. Moreover compounds with Excited-State Intramolecular Proton Transfer (ESIPT) are in the focus of the interest of scientists throughout the world, because dual fluorescence spectra of such objects corresponding to two forms of molecular structure (normal and photoproduct) are very sensitive to characteristics of molecular microenvironment. This property allows to use such substances as fluorescent probes for diverse applications in chemistry and Life Sciences. But at the same time studying of proton transfer processes is not simple, because this process is characterized by extremely fast times (on picoseconds time scale and less order) and very often contribution of reverse reactions is essentially complicates an interpretation of observed properties of dual fluorescence. Hence, understanding of a role of reversible reactions is crucial for a comprehensive description of all processes accompanying excited state reactions. We discuss new approach for treatment ESIPT reaction on the basis of experimentally measured instant spectra of dual fluorescence and temporal behavior of ratiometric signal of normal to tautomer form intensities. Simple analytical expressions show in transparent way how to distinguish a degree of reverse reaction contribution to ratiometric signal. A validation of the approach under consideration is fulfilled with two different flavonols – 3-hydroxyflavone and 4′-(Dimethylamino)-3-hydroxyflavone – representing two extreme cases in affecting reversible reaction on dual emission. A comparing of new approach and traditional method when we analyze kinetics of separate the N* and T* fluorescence bands decays, has been carried out. - Highlights: • The excited

  3. Thermo-Kinetic Investigation of Comparative Ligand Effect on Cysteine Iron Redox Reaction

    OpenAIRE

    Rizvi, Masood Ahmad; Teshima, Norio; Maqsood, Syed Raashid; Akhoon, Showket Ahmad; Peerzada, Ghulam Mustafa

    2015-01-01

    Transition metal ions in their free state bring unwanted biological oxidations generating oxidative stress. The ligand modulated redox potential can be indispensable in prevention of such oxidative stress by blocking the redundant bio-redox reactions. In this study we investigated the comparative ligand effect on the thermo-kinetic aspects of biologically important cysteine iron (III) redox reaction using spectrophotometric and potentiometric methods. The results were corroborated...

  4. On the Mathematical Structure of Balanced Chemical Reaction Networks Governed by Mass Action Kinetics

    NARCIS (Netherlands)

    Schaft, Arjan van der; Rao, Shodhan; Jayawardhana, Bayu

    2013-01-01

    Motivated by recent progress on the interplay between graph theory, dynamics, and systems theory, we revisit the analysis of chemical reaction networks described by mass action kinetics. For reaction networks possessing a thermodynamic equilibrium we derive a compact formulation exhibiting at the

  5. BGK-type models in strong reaction and kinetic chemical equilibrium regimes

    International Nuclear Information System (INIS)

    Monaco, R; Bianchi, M Pandolfi; Soares, A J

    2005-01-01

    A BGK-type procedure is applied to multi-component gases undergoing chemical reactions of bimolecular type. The relaxation process towards local Maxwellians, depending on mass and numerical densities of each species as well as common velocity and temperature, is investigated in two different cases with respect to chemical regimes. These cases are related to the strong reaction regime characterized by slow reactions, and to the kinetic chemical equilibrium regime where fast reactions take place. The consistency properties of both models are stated in detail. The trend to equilibrium is numerically tested and comparisons for the two regimes are performed within the hydrogen-air and carbon-oxygen reaction mechanism. In the spatial homogeneous case, it is also shown that the thermodynamical equilibrium of the models recovers satisfactorily the asymptotic equilibrium solutions to the reactive Euler equations

  6. Kinetic aspects of the embedded clusters: Reaction - Rate Theory

    International Nuclear Information System (INIS)

    Despa, F.; Apostol, M.

    1995-07-01

    The main stages of the cluster growth process are reviewed using Reaction - Rate Theory. The precipitation stage is shown as a relaxation of the solute towards a cluster state characterized by a higher stability. The kinetic of the late stage of phase separation, the coarsening process, is analyzed by an off-centre diffusion mechanism. The theoretical results are compared to the experimental ones. (author). 37 refs, 6 figs

  7. Heterogeneous photocatalysis of real textile wastewater: evaluation of reaction kinetics and characterization.

    Science.gov (United States)

    Sahoo, Chittaranjan; Gupta, Ashok K; Pillai, Indu M Sasidharan

    2012-01-01

    Real textile wastewater collected from the cotton dyeing bath of a fabric dyeing and finishing plant was subjected to heterogeneous photocatalysis using Ag(+) doped TiO(2) under UV irradiation in a batch reactor. The photocatalysts were characterized by FESEM, XRD, EDS, FTIR, DRS and BET analyses. The kinetics of the reaction was also evaluated. Colour removal was more than 88%, 94% and 99%, respectively for undiluted, 2 times diluted and 5 times diluted wastewater with Ag(+) doped TiO(2) (2.5 g/L) after UV irradiation for 360 minutes. The COD removal for undiluted, 2 times diluted and 5 times diluted wastewater was 47%, 70% and 92%, respectively under similar conditions. The reaction followed Langmuir-Hinshelwood pseudo first order kinetic model and the data fitted well to polynomial regression analysis.

  8. Multiresponse kinetic modelling of Maillard reaction and caramelisation in a heated glucose/wheat flour system.

    Science.gov (United States)

    Kocadağlı, Tolgahan; Gökmen, Vural

    2016-11-15

    The study describes the kinetics of the formation and degradation of α-dicarbonyl compounds in glucose/wheat flour system heated under low moisture conditions. Changes in the concentrations of glucose, fructose, individual free amino acids, lysine and arginine residues, glucosone, 1-deoxyglucosone, 3-deoxyglucosone, 3,4-dideoxyglucosone, 5-hydroxymethyl-2-furfural, glyoxal, methylglyoxal and diacetyl concentrations were determined to form a multiresponse kinetic model for isomerisation and degradation reactions of glucose. Degradation of Amadori product mainly produced 1-deoxyglucosone. Formation of 3-deoxyglucosone proceeded directly from glucose and also Amadori product degradation. Glyoxal formation was predominant from glucosone while methylglyoxal and diacetyl originated from 1-deoxyglucosone. Formation of 5-hydroxymethyl-2-furfural from fructose was found to be a key step. Multi-response kinetic modelling of Maillard reaction and caramelisation simultaneously indicated quantitatively predominant parallel and consecutive pathways and rate limiting steps by estimating the reaction rate constants. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. A study of butyl acetate synthesis. 4-reaction kinetics

    Directory of Open Access Journals (Sweden)

    Álvaro Orjuela Londoño

    2006-05-01

    Full Text Available This work was aimed at studying liquid-phase acetic acid and butyl alcohol esterification reaction (P atm =0.76 Bar,using an ion exchange resin (Lewatit K-2431 as catalyst. The effect of the absence of internal and external mass transport on catalyst particles was established in the research conditions used here. A set of assays to determine the effect of catalyst load (0.5%, 1%, 2% w/w temperature (73°C, 80°C, 87°C and molar ratio (1:2, 1:1, 2:1 acid/alcohol on reaction rate was carried out and both LHHW and pseudo-homogeneous kinetic expressions were obtained, these being in good agreement with the experimental data.

  10. Diagnostic Appraisal of Grade 12 Students' Understanding of Reaction Kinetics

    Science.gov (United States)

    Yan, Yaw Kai; Subramaniam, R.

    2016-01-01

    The study explored grade 12 students' understanding of reaction kinetics, a topic which has not been extensively explored in the chemistry education literature at this level. A 3-tier diagnostic instrument with 11 questions was developed--this format is of very recent origin and has been the subject of only a handful of studies. The findings…

  11. Kinetic investigation of the chlorine reduction reaction on electrochemically oxidised ruthenium

    International Nuclear Information System (INIS)

    Thomassen, M.; Karlsen, C.; Borresen, B.; Tunold, R.

    2006-01-01

    The rate and mechanism of the electroreduction of chlorine on electrooxidised ruthenium has been investigated with focus on the effect of solution pH. Current/potential curves for the reduction process in solutions with constant chloride concentration of 1.0 mol dm -3 and varying H + concentration have been obtained with the use of the rotating disk electrode technique (RDE). It was found that the chlorine reduction rate is highly inhibited in solutions with high H + concentrations and that it can be satisfactorily described by the Erenburg mechanism, previously suggested for the chlorine evolution on RuO 2 and RTO. The expression of the kinetic current as a function of chlorine and H + concentration was obtained by solving the elementary rate equations of the kinetic mechanism. The kinetic constants obtained from the correlation of the kinetic current expression to the experimental data were used to simulate the dependence of the surface coverages and elementary reaction rates on overpotential

  12. Bacillus anthracis o-succinylbenzoyl-CoA synthetase: reaction kinetics and a novel inhibitor mimicking its reaction intermediate.

    Science.gov (United States)

    Tian, Yang; Suk, Dae-Hwan; Cai, Feng; Crich, David; Mesecar, Andrew D

    2008-11-25

    o-Succinylbenzoyl-CoA (OSB-CoA) synthetase (EC 6.2.1.26) catalyzes the ATP-dependent condensation of o-succinylbenzoate (OSB) and CoA to form OSB-CoA, the fourth step of the menaquinone biosynthetic pathway in Bacillus anthracis. Gene knockout studies have highlighted this enzyme as a potential target for the discovery of new antibiotics. Here we report the first studies on the kinetic mechanism of B. anthracis OSB-CoA synthetase, classifying it as an ordered bi uni uni bi ping-pong mechanism. Through a series of pre-steady-state and steady-state kinetic studies in conjunction with direct binding studies, it is demonstrated that CoA, the last substrate to bind, strongly activates the first half-reaction after the first round of turnover. The activation of the first half-reaction is most likely achieved by CoA stabilizing conformations of the enzyme in the "F" form, which slowly isomerize back to the E form. Thus, the kinetic mechanism of OSB-CoA synthetase may be more accurately described as an ordered bi uni uni bi iso ping-pong mechanism. The substrate specificity of OSB-CoA synthetase was probed using a series of OSB analogues with alterations in the carboxylate groups. OSB-CoA shows a strong preference for OSB over all of the analogues tested as none were active except 4-[2-(trifluoromethyl)phenyl]-4-oxobutyric acid which exhibited a 100-fold decrease in k(cat)/K(m). On the basis of an understanding of OSB-CoA synthetase's kinetic mechanism and substrate specificity, a reaction intermediate analogue of OSB-AMP, 5'-O-{N-[2-(trifluoromethyl)phenyl]-4-oxobutyl}adenosine sulfonamide (TFMP-butyl-AMS), was designed and synthesized. This inhibitor was found to be an uncompetitive inhibitor to CoA and a mixed-type inhibitor to ATP and OSB with low micromolar inhibition constants. Collectively, these results should serve as an important forerunner to more detailed and extensive inhibitor design studies aimed at developing lead compounds against the OSB-CoA synthetase

  13. 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.

  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

    2018-06-01

    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.

  15. 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

  16. Constrained reaction volume approach for studying chemical kinetics behind reflected shock waves

    KAUST Repository

    Hanson, Ronald K.; Pang, Genny A.; Chakraborty, Sreyashi; Ren, Wei; Wang, Shengkai; Davidson, David Frank

    2013-01-01

    We report a constrained-reaction-volume strategy for conducting kinetics experiments behind reflected shock waves, achieved in the present work by staged filling in a shock tube. Using hydrogen-oxygen ignition experiments as an example, we

  17. The Nanoconfined Free Radical Polymerization: Reaction Kinetics and Thermodynamics

    Science.gov (United States)

    Zhao, Haoyu; Simon, Sindee

    The reaction kinetics and thermodynamics of nanoconfined free radical polymerizations are investigated for methyl methacrylate (MMA) and ethyl methacrylate (EMA) monomers using differential scanning calorimetry. Controlled pore glass is used as the confinement medium with pore diameters as small as 7.5 nm; the influence of both hydrophobic (silanized such that trimethylsilyl groups cover the surface) and hydrophilic (native silanol) surfaces is investigated. Propagation rates increase when monomers are reacted in the hydrophilic pores presumably due to the specific interactions between the carbonyl and silanol groups; however, the more flexible EMA monomer shows weaker effects. On the other hand, initial rates of polymerization in hydrophobic pores are unchanged from the bulk. In both pores, the onset of autoacceleration occurs earlier due to the reduced diffusivity of confined chains, which may be compensated at high temperatures. In addition to changes in kinetics, the reaction thermodynamics can be affected under nanoconfinement. Specifically, the ceiling temperature (Tc) is shifted to lower temperatures in nanopores, with pore surface chemistry showing no significant effects; the equilibrium conversion is also reduced at high temperatures below Tc. These observations are attributed to a larger negative change in entropy on propagation for the confined system, with the MMA system again showing greater effects. Funding from ACS PRF is gratefully acknowledged.

  18. Determination of kinetic parameters of heterogeneous isotopic exchange reaction

    International Nuclear Information System (INIS)

    Huang, Ting-Chia; Tsai, Fuan-Nan

    1977-01-01

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

  19. Pressure-dependent kinetics of initial reactions in iso-octane pyrolysis.

    Science.gov (United States)

    Ning, HongBo; Gong, ChunMing; Li, ZeRong; Li, XiangYuan

    2015-05-07

    This study focuses on the studies of the main pressure-dependent reaction types of iso-octane (iso-C8H18) pyrolysis, including initial C-C bond fission of iso-octane, isomerization, and β-scission reactions of the alkyl radicals produced by the C-C bond fission of iso-octane. For the C-C bond fission of iso-octane, the minimum energy potentials are calculated at the CASPT2(2e,2o)/6-31+G(d,p)//CAS(2e,2o)/6-31+G(d,p) level of theory. For the isomerization and the β-scission reactions of the alkyl radicals, the optimization of the geometries and the vibrational frequencies of the reactants, transition states, and products are performed at the B3LYP/CBSB7 level, and their single point energies are calculated by using the composite CBS-QB3 method. Variable reaction coordinate transition state theory (VRC-TST) is used for the high-pressure limit rate constant calculation and Rice-Ramsperger-Kassel-Marcus/master equation (RRKM/ME) is used to calculate the pressure-dependent rate constants of these channels with pressure varying from 0.01-100 atm. The rate constants obtained in this work are in good agreement with those available from literatures. We have updated the rate constants and thermodynamic parameters for species involved in these reactions into a current chemical kinetic mechanism and also have improved the concentration profiles of main products such as C3H6 and C4H6 in the shock tube pyrolysis of iso-octane. The results of this study provide insight into the pyrolysis of iso-octane and will be helpful in the future development of branched paraffin kinetic mechanisms.

  20. Thermodynamic and kinetic properties of hydrogen defect pairs in SrTiO3 from density functional theory

    DEFF Research Database (Denmark)

    Bork, Nicolai Christian; Bonanos, Nikolaos; Rossmeisl, Jan

    2011-01-01

    A density functional theory investigation of the thermodynamic and kinetic properties of hydrogen–hydrogen defect interactions in the cubic SrTiO3 perovskite is presented. We find a net attraction between two hydrogen atoms with an optimal separation of ∼2.3 Å. The energy gain is ca. 0.33 eV comp...

  1. Optimization and kinetic studies of sea mango (Cerbera odollam) oil for biodiesel production via supercritical reaction

    International Nuclear Information System (INIS)

    Ang, Gaik Tin; Ooi, San Nee; Tan, Kok Tat; Lee, Keat Teong; Mohamed, Abdul Rahman

    2015-01-01

    Highlights: • Sea mango oil as feedstock for biodiesel via non-catalytic supercritical reaction. • Extracted sea mango oil with high FFA could produce high yield of FAME. • Employment of Response Surface Methodology for optimization of FAME. • Kinetic study for reversible transesterification and esterification reactions. - Abstract: Sea mango (Cerbera odollam) oil, which is rich in free fatty acids, was utilized to produce fatty acid methyl esters (FAME) via supercritical transesterification reaction. Sea mango oil was extracted from seeds and was subsequently reacted with methanol in a batch-type supercritical reactor. Response surface methodology (RSM) analysis was used to optimize important parameters, including reaction temperature, reaction time and the molar ratio of methanol to oil. The optimum conditions were found as 380 °C, 40 min and 45:1 mol/mol, respectively, to achieve 78% biodiesel content. The first kinetic modelling of FAME production from sea mango oil incorporating reversible transesterification and reversible esterification was verified simultaneously. The kinetic parameters, including reaction rate constants, k, the pre-exponential constant, A, and the activation energy, Ea, for transesterification and esterification were determined using an ordinary differential equation (ODE45) solver. The highest activation energy of 40 kJ/mol and the lowest reaction rate constant of 2.50 × 10 −5 dm 3 /mol s verified that the first stepwise reaction of TG to produce DG was the rate-limiting step

  2. Gas phase polymerization of propylene. Reaction kinetics and molecular weight distribution

    NARCIS (Netherlands)

    Meier, G.B.; Weickert, G.; van Swaaij, Willibrordus Petrus Maria

    2001-01-01

    Gas-phase polymerizations have been executed at different temperatures, pressures, and hydrogen concentrations using Me2Si[Ind]2ZrCl2 / methylaluminoxane / SiO2(Pennsylvania Quarts) as a catalyst. The reaction rate curves have been described by a kinetic model, which takes into account the initially

  3. Constrained reaction volume approach for studying chemical kinetics behind reflected shock waves

    KAUST Repository

    Hanson, Ronald K.

    2013-09-01

    We report a constrained-reaction-volume strategy for conducting kinetics experiments behind reflected shock waves, achieved in the present work by staged filling in a shock tube. Using hydrogen-oxygen ignition experiments as an example, we demonstrate that this strategy eliminates the possibility of non-localized (remote) ignition in shock tubes. Furthermore, we show that this same strategy can also effectively eliminate or minimize pressure changes due to combustion heat release, thereby enabling quantitative modeling of the kinetics throughout the combustion event using a simple assumption of specified pressure and enthalpy. We measure temperature and OH radical time-histories during ethylene-oxygen combustion behind reflected shock waves in a constrained reaction volume and verify that the results can be accurately modeled using a detailed mechanism and a specified pressure and enthalpy constraint. © 2013 The Combustion Institute.

  4. Using a Multi-Tier Diagnostic Test to Explore the Nature of Students' Alternative Conceptions on Reaction Kinetics

    Science.gov (United States)

    Yan, Yaw Kai; Subramaniam, R.

    2018-01-01

    This study focused on grade 12 students' understanding of reaction kinetics. A 4-tier diagnostic instrument was developed for this purpose and administered to 137 students in the main study. Findings showed that reaction kinetics is a difficult topic for these students, with a total of 25 alternative conceptions (ACs) being uncovered. Except for…

  5. Annealing Kinetic Model Using Fast and Slow Metastable Defects for Hydrogenated-Amorphous-Silicon-Based Solar Cells

    Directory of Open Access Journals (Sweden)

    Seung Yeop Myong

    2007-01-01

    Full Text Available The two-component kinetic model employing “fast” and “slow” metastable defects for the annealing behaviors in pin-type hydrogenated-amorphous-silicon- (a-Si:H- based solar cells is simulated using a normalized fill factor. Reported annealing data on pin-type a-Si:H-based solar cells are revisited and fitted using the model to confirm its validity. It is verified that the two-component model is suitable for fitting the various experimental phenomena. In addition, the activation energy for annealing of the solar cells depends on the definition of the recovery time. From the thermally activated and high electric field annealing behaviors, the plausible microscopic mechanism on the defect removal process is discussed.

  6. 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.

  7. Presenting a new kinetic model for methanol to light olefins reactions over a hierarchical SAPO-34 catalyst using the Langmuir-Hinshelwood-Hougen-Watson mechanism

    Science.gov (United States)

    Javad Azarhoosh, Mohammad; Halladj, Rouein; Askari, Sima

    2017-10-01

    In this study, a new kinetic model for methanol to light olefins (MTO) reactions over a hierarchical SAPO-34 catalyst using the Langmuir-Hinshelwood-Hougen-Watson (LHHW) mechanism was presented and the kinetic parameters was obtained using a genetic algorithm (GA) and genetic programming (GP). Several kinetic models for the MTO reactions have been presented. However, due to the complexity of the reactions, most reactions are considered lumped and elementary, which cannot be deemed a completely accurate kinetic model of the process. Therefore, in this study, the LHHW mechanism is presented as kinetic models of MTO reactions. Because of the non-linearity of the kinetic models and existence of many local optimal points, evolutionary algorithms (GA and GP) are used in this study to estimate the kinetic parameters in the rate equations. Via the simultaneous connection of the code related to modelling the reactor and the GA and GP codes in the MATLAB R2013a software, optimization of the kinetic models parameters was performed such that the least difference between the results from the kinetic models and experiential results was obtained and the best kinetic parameters of MTO process reactions were achieved. A comparison of the results from the model with experiential results showed that the present model possesses good accuracy.

  8. A study of redox kinetic in silicate melt; Etude cinetique des reactions d'oxydoreduction dans les silicates

    Energy Technology Data Exchange (ETDEWEB)

    Magnien, V

    2005-12-15

    The aim of this thesis is to understand better iron redox reactions and mechanisms in silicate glasses and melts. Particular interest has been paid to the influence of temperature and chemical composition. For this purpose, the influence of alkali element content, iron content and network formers on the kinetics of redox reactions has been determined through XANES and Raman spectroscopy experiments performed either near the glass transition or above the liquidus temperature. As a complement, electrical conductivity and RBS spectroscopy experiments have been made to characterize the diffusivity of the species that transport electrical charges and the reaction morphology, respectively. Temperature and composition variations can induce changes in the dominating redox mechanism. At a given temperature, the parameters that exert the strongest influence on redox mechanisms are the presence or lack of divalent cations and the existing decoupling between the mobility of network former and modifier elements. Near Tg, the diffusion of divalent cations, when present in the melt, controls the kinetics of iron redox reactions along with a flux of electron holes. Composition, through the degree of polymerization and the silicate network structure, influences the kinetics and the nature of the involved cations, but not the mechanisms of the reaction. Without alkaline earth elements, the kinetics of redox reactions are controlled by the diffusion of oxygen species. With increasing temperatures, the diffusivities of all ionic species tend to become similar. The decoupling between ionic fluxes then is reduced so that several mechanisms become kinetically equivalent and can thus coexist. (author)

  9. Displacement cascades and defect annealing in tungsten, Part III: The sensitivity of cascade annealing in tungsten to the values of kinetic parameters

    Energy Technology Data Exchange (ETDEWEB)

    Nandipati, Giridhar; Setyawan, Wahyu; Heinisch, Howard L.; Roche, Kenneth J.; Kurtz, Richard J.; Wirth, Brian D.

    2015-07-01

    Object kinetic Monte Carlo (OKMC) simulations have been performed to investigate various aspects of cascade aging in bulk tungsten and to determine the sensitivity of the results to the kinetic parameters. The primary focus is on how the kinetic parameters affect the initial recombination of defects in the first few ns of a simulation. The simulations were carried out using the object kinetic Monte Carlo (OKMC) code KSOME (kinetic simulations of microstructure evolution), using a database of cascades obtained from results of molecular dynamics (MD) simulations at various primary knock-on atom (PKA) energies and directions at temperatures of 300, 1025 and 2050 K. The OKMC model was parameterized using defect migration barriers and binding energies from ab initio calculations. Results indicate that, due to the disparate mobilities of SIA and vacancy clusters in tungsten, annealing is dominated by SIA migration even at temperatures as high as 2050 K. For 100 keV cascades initiated at 300 K recombination is dominated by annihilation of large defect clusters. But for all other PKA energies and temperatures most of the recombination is due to the migration and rotation of small SIA clusters, while all the large SIA clusters escape the cubic simulation cell. The inverse U-shape behavior exhibited by the annealing efficiency as a function of temperature curve, especially for cascades of large PKA energies, is due to asymmetry in SIA and vacancy clustering assisted by the large difference in mobilities of SIAs and vacancies. This annealing behavior is unaffected by the dimensionality of SIA migration persists over a broad range of relative mobilities of SIAs and vacancies.

  10. Kinetics based reaction optimization of enzyme catalyzed reduction of formaldehyde to methanol with synchronous cofactor regeneration.

    Science.gov (United States)

    Marpani, Fauziah; Sárossy, Zsuzsa; Pinelo, Manuel; Meyer, Anne S

    2017-12-01

    Enzymatic reduction of carbon dioxide (CO 2 ) to methanol (CH 3 OH) can be accomplished using a designed set-up of three oxidoreductases utilizing reduced pyridine nucleotide (NADH) as cofactor for the reducing equivalents electron supply. For this enzyme system to function efficiently a balanced regeneration of the reducing equivalents during reaction is required. Herein, we report the optimization of the enzymatic conversion of formaldehyde (CHOH) to CH 3 OH by alcohol dehydrogenase, the final step of the enzymatic redox reaction of CO 2 to CH 3 OH, with kinetically synchronous enzymatic cofactor regeneration using either glucose dehydrogenase (System I) or xylose dehydrogenase (System II). A mathematical model of the enzyme kinetics was employed to identify the best reaction set-up for attaining optimal cofactor recycling rate and enzyme utilization efficiency. Targeted process optimization experiments were conducted to verify the kinetically modeled results. Repetitive reaction cycles were shown to enhance the yield of CH 3 OH, increase the total turnover number (TTN) and the biocatalytic productivity rate (BPR) value for both system I and II whilst minimizing the exposure of the enzymes to high concentrations of CHOH. System II was found to be superior to System I with a yield of 8 mM CH 3 OH, a TTN of 160 and BPR of 24 μmol CH 3 OH/U · h during 6 hr of reaction. The study demonstrates that an optimal reaction set-up could be designed from rational kinetics modeling to maximize the yield of CH 3 OH, whilst simultaneously optimizing cofactor recycling and enzyme utilization efficiency. © 2017 Wiley Periodicals, Inc.

  11. Thermodynamic and Kinetic Response of Microbial Reactions to High CO2.

    Science.gov (United States)

    Jin, Qusheng; Kirk, Matthew F

    2016-01-01

    Geological carbon sequestration captures CO 2 from industrial sources and stores the CO 2 in subsurface reservoirs, a viable strategy for mitigating global climate change. In assessing the environmental impact of the strategy, a key question is how microbial reactions respond to the elevated CO 2 concentration. This study uses biogeochemical modeling to explore the influence of CO 2 on the thermodynamics and kinetics of common microbial reactions in subsurface environments, including syntrophic oxidation, iron reduction, sulfate reduction, and methanogenesis. The results show that increasing CO 2 levels decreases groundwater pH and modulates chemical speciation of weak acids in groundwater, which in turn affect microbial reactions in different ways and to different extents. Specifically, a thermodynamic analysis shows that increasing CO 2 partial pressure lowers the energy available from syntrophic oxidation and acetoclastic methanogenesis, but raises the available energy of microbial iron reduction, hydrogenotrophic sulfate reduction and methanogenesis. Kinetic modeling suggests that high CO 2 has the potential of inhibiting microbial sulfate reduction while promoting iron reduction. These results are consistent with the observations of previous laboratory and field studies, and highlight the complexity in microbiological responses to elevated CO 2 abundance, and the potential power of biogeochemical modeling in evaluating and quantifying these responses.

  12. Thermodynamic and kinetic response of microbial reactions to high CO2

    Directory of Open Access Journals (Sweden)

    Qusheng Jin

    2016-11-01

    Full Text Available Geological carbon sequestration captures CO2 from industrial sources and stores the CO2 in subsurface reservoirs, a viable strategy for mitigating global climate change. In assessing the environmental impact of the strategy, a key question is how microbial reactions respond to the elevated CO2 concentration. This study uses biogeochemical modeling to explore the influence of CO2 on the thermodynamics and kinetics of common microbial reactions in subsurface environments, including syntrophic oxidation, iron reduction, sulfate reduction, and methanogenesis. The results show that increasing CO2 levels decreases groundwater pH and modulates chemical speciation of weak acids in groundwater, which in turn affect microbial reactions in different ways and to different extents. Specifically, a thermodynamic analysis shows that increasing CO2 partial pressure lowers the energy available from syntrophic oxidation and acetoclastic methanogenesis, but raises the available energy of microbial iron reduction, hydrogenotrophic sulfate reduction and methanogenesis. Kinetic modeling suggests that high CO2 has the potential of inhibiting microbial sulfate reduction while promoting iron reduction. These results are consistent with the observations of previous laboratory and field studies, and highlight the complexity in microbiological responses to elevated CO2 abundance, and the potential power of biogeochemical modeling in evaluating and quantifying these responses.

  13. Bayesian inference of chemical kinetic models from proposed reactions

    KAUST Repository

    Galagali, Nikhil

    2015-02-01

    © 2014 Elsevier Ltd. Bayesian inference provides a natural framework for combining experimental data with prior knowledge to develop chemical kinetic models and quantify the associated uncertainties, not only in parameter values but also in model structure. Most existing applications of Bayesian model selection methods to chemical kinetics have been limited to comparisons among a small set of models, however. The significant computational cost of evaluating posterior model probabilities renders traditional Bayesian methods infeasible when the model space becomes large. We present a new framework for tractable Bayesian model inference and uncertainty quantification using a large number of systematically generated model hypotheses. The approach involves imposing point-mass mixture priors over rate constants and exploring the resulting posterior distribution using an adaptive Markov chain Monte Carlo method. The posterior samples are used to identify plausible models, to quantify rate constant uncertainties, and to extract key diagnostic information about model structure-such as the reactions and operating pathways most strongly supported by the data. We provide numerical demonstrations of the proposed framework by inferring kinetic models for catalytic steam and dry reforming of methane using available experimental data.

  14. Influence of Proton Acceptors on the Proton-Coupled Electron Transfer Reaction Kinetics of a Ruthenium-Tyrosine Complex.

    Science.gov (United States)

    Lennox, J Christian; Dempsey, Jillian L

    2017-11-22

    A polypyridyl ruthenium complex with fluorinated bipyridine ligands and a covalently bound tyrosine moiety was synthesized, and its photo-induced proton-coupled electron transfer (PCET) reactivity in acetonitrile was investigated with transient absorption spectroscopy. Using flash-quench methodology with methyl viologen as an oxidative quencher, a Ru 3+ species is generated that is capable of initiating the intramolecular PCET oxidation of the tyrosine moiety. Using a series of substituted pyridine bases, the reaction kinetics were found to vary as a function of proton acceptor concentration and identity, with no significant H/D kinetic isotope effect. Through analysis of the kinetics traces and comparison to a control complex without the tyrosine moiety, PCET reactivity was found to proceed through an equilibrium electron transfer followed by proton transfer (ET-PT) pathway in which irreversible deprotonation of the tyrosine radical cation shifts the ET equilibrium, conferring a base dependence on the reaction. Comprehensive kinetics modeling allowed for deconvolution of complex kinetics and determination of rate constants for each elementary step. Across the five pyridine bases explored, spanning a range of 4.2 pK a units, a linear free-energy relationship was found for the proton transfer rate constant with a slope of 0.32. These findings highlight the influence that proton transfer driving force exerts on PCET reaction kinetics.

  15. Kinetics of the reaction between H· and superheated water probed with muonium

    International Nuclear Information System (INIS)

    Alcorn, C.; Brodovitch, J.-C.; Ghandi, K.; Kennedy, A.; Percival, P.W.; Smith, M.

    2011-01-01

    Safe operation of a supercritical water cooled reactor requires knowledge of the reaction kinetics of transient species formed by the radiolysis of water in the temperature range 300-650"oC. By using a light isotope of the H·atom, it is possible to study its chemistry in water over this range of temperatures. Arguably, the most important reaction to study is that of the H·atom with the bulk solvent. This reaction could provide an in situ source of H_2 gas, which is added to CANDU reactors to suppress oxidative corrosion. The work described here concerns studies of the reaction of muonium with H_2O and D_2O at temperatures up to 450"oC.

  16. Bacillus anthracis o-succinylbenzoyl-CoA synthetase: reaction kinetics and a novel inhibitor mimicking its reaction intermediate †

    Science.gov (United States)

    Tian, Yang; Suk, Dae-Hwan; Cai, Feng; Crich, David; Mesecar, Andrew D.

    2009-01-01

    O-succinylbenzoyl-CoA (OSB-CoA) synthetase (EC 6.2.1.26) catalyzes the ATP-dependent condensation of o-succinylbenzoate (OSB) and CoA to form OSB-CoA, the fourth step of the menaquinone biosynthetic pathway in Bacillus anthracis. Gene knockout studies have highlighted this enzyme as a potential target for the discovery of new antibiotics. Here we report the first studies on the kinetic mechanism of B. anthracis OSB-CoA synthetase, classifying it as an ordered Bi Uni Uni Bi ping-pong mechanism. Through a series of pre-steady-state and steady-state kinetic studies in conjunction with direct-binding studies, it is demonstrated that CoA, the last substrate to bind, strongly activates the first half-reaction after the first round of turnover. The activation of the first-half reaction is most likely achieved by CoA stabilizing conformations of the enzyme in the ‘F’ form, which slowly isomerize back to the E form. Thus, the kinetic mechanism of OSB-CoA synthetase may be more accurately described as an ordered Bi Uni Uni Bi Iso ping-pong mechanism. The substrate specificity of OSB-CoA synthetase was probed using a series of OSB analogs with alterations in the carboxylate groups. OSB-CoA shows a strong preference for OSB over all of the analogs tested as none were active except 4-(2-trifluoromethylphenyl)-4-oxobutyric acid which exhibited a 100-fold decrease in kcat/Km. Based on an understanding of OSB-CoA synthetase’s kinetic mechanism and substrate specificity, a reaction intermediate analog of OSB-AMP, 5’-O-(N-(2-trifluoromethylphenyl)-4-oxobutyl) adenosine sulfonamide (TFMP-butyl-AMS), was designed and synthesized. This inhibitor was found to be an uncompetitive inhibitor to CoA and a mixed-type inhibitor to ATP and OSB with low micromolar inhibition constants. Collectively, these results should serve as an important forerunner to more detailed and extensive inhibitor design studies aimed at developing lead compounds against the OSB-CoA synthetase class of

  17. Stepwise kinetic equilibrium models of quantitative polymerase chain reaction

    Directory of Open Access Journals (Sweden)

    Cobbs Gary

    2012-08-01

    Full Text Available Abstract Background Numerous models for use in interpreting quantitative PCR (qPCR data are present in recent literature. The most commonly used models assume the amplification in qPCR is exponential and fit an exponential model with a constant rate of increase to a select part of the curve. Kinetic theory may be used to model the annealing phase and does not assume constant efficiency of amplification. Mechanistic models describing the annealing phase with kinetic theory offer the most potential for accurate interpretation of qPCR data. Even so, they have not been thoroughly investigated and are rarely used for interpretation of qPCR data. New results for kinetic modeling of qPCR are presented. Results Two models are presented in which the efficiency of amplification is based on equilibrium solutions for the annealing phase of the qPCR process. Model 1 assumes annealing of complementary targets strands and annealing of target and primers are both reversible reactions and reach a dynamic equilibrium. Model 2 assumes all annealing reactions are nonreversible and equilibrium is static. Both models include the effect of primer concentration during the annealing phase. Analytic formulae are given for the equilibrium values of all single and double stranded molecules at the end of the annealing step. The equilibrium values are then used in a stepwise method to describe the whole qPCR process. Rate constants of kinetic models are the same for solutions that are identical except for possibly having different initial target concentrations. Analysis of qPCR curves from such solutions are thus analyzed by simultaneous non-linear curve fitting with the same rate constant values applying to all curves and each curve having a unique value for initial target concentration. The models were fit to two data sets for which the true initial target concentrations are known. Both models give better fit to observed qPCR data than other kinetic models present in the

  18. Stepwise kinetic equilibrium models of quantitative polymerase chain reaction.

    Science.gov (United States)

    Cobbs, Gary

    2012-08-16

    Numerous models for use in interpreting quantitative PCR (qPCR) data are present in recent literature. The most commonly used models assume the amplification in qPCR is exponential and fit an exponential model with a constant rate of increase to a select part of the curve. Kinetic theory may be used to model the annealing phase and does not assume constant efficiency of amplification. Mechanistic models describing the annealing phase with kinetic theory offer the most potential for accurate interpretation of qPCR data. Even so, they have not been thoroughly investigated and are rarely used for interpretation of qPCR data. New results for kinetic modeling of qPCR are presented. Two models are presented in which the efficiency of amplification is based on equilibrium solutions for the annealing phase of the qPCR process. Model 1 assumes annealing of complementary targets strands and annealing of target and primers are both reversible reactions and reach a dynamic equilibrium. Model 2 assumes all annealing reactions are nonreversible and equilibrium is static. Both models include the effect of primer concentration during the annealing phase. Analytic formulae are given for the equilibrium values of all single and double stranded molecules at the end of the annealing step. The equilibrium values are then used in a stepwise method to describe the whole qPCR process. Rate constants of kinetic models are the same for solutions that are identical except for possibly having different initial target concentrations. Analysis of qPCR curves from such solutions are thus analyzed by simultaneous non-linear curve fitting with the same rate constant values applying to all curves and each curve having a unique value for initial target concentration. The models were fit to two data sets for which the true initial target concentrations are known. Both models give better fit to observed qPCR data than other kinetic models present in the literature. They also give better estimates of

  19. Kinetic study of the annealing reactions in Cu-Ni-Fe alloys

    International Nuclear Information System (INIS)

    Donoso, E.

    2014-01-01

    The thermal aging of a Cu-45Ni-4Fe, Cu-34Ni-11Fe and Cu-33Ni-22Fe alloys tempered from 1173 K have been studied from Differential Scanning Calorimetry (DSC) and microhardness measurements. The analysis of DSC curves, from room temperature to 950 K, shows the presence of one exothermic reaction associated to the formation of FeNi 3 phase nucleating from a modulate structure, and one endothermic peak attributed to dissolution of this phase. Kinetic parameters were obtained using the usual Avrami-Erofeev equation, modified Kissinger method and integrated kinetic functions. Microhardness measurements confirmed the formation and dissolution of the FeNi 3 phase. (Author)

  20. Kinetics and mechanism of the gas phase reaction of Cl atoms with iodobenzene

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbæk; Ponomarev, DA; Nielsen, OJ

    2001-01-01

    Smog chamber/FTIR techniques were used to study the kinetics and mechanism of the reaction of Cl atoms with iodobenzene (C6H5I) in 20-700 Torr of N-2, air, or O-2 diluent at 296 K. The reaction proceeds with a rate constant k(Cl + QH(5)I) = (3.3 +/- 0.7) x 10(-11) cm(3) molecule(-1) s(-1) to give...

  1. Kinetic and mechanism formation reaction of complex compound Cu with di-n-buthildithiocarbamate (dbdtc) ligand

    Science.gov (United States)

    Haryani, S.; Kurniawan, C.; Kasmui

    2018-04-01

    Synthesis of complex compound is one field of research which intensively studied. Metal-dithiocarbamate complexes find wide-ranging applications in nanomaterial and metal separation science, and have potential use as chemotherapeutic, pesticides, and as additives to lubricants. However, the information about is reaction kinetic and mechanism are very much lacking. The research and analyzes results show that reaction synthesis ligand DBDTC and complex compounds Cu-DBDTC. Optimum reaction condition of formation of complex compounds Cu with DBDTC at pH=3, [DBDTC] = 4.10-3 M, and the time of reaction 5 minutes. Based the analysis varian reaction of complex compounds at pH 3 and 4, diffrence significance at the other pH: 5; 5,5; 6; 6,5 ; 7; and 8. The various of mole with reactants comosition difference sigbificance, those the time reaction for 5 and 6 minutes diffrence by significance with the other time, it is 3,4,8, and 10 minutes. The great product to at condition pH 6, the time optimum at 5 minutes and molar ratio of logam: ligand = 1:2. The reaction kinetic equation of complex compound Cu with chelathing ligand DBDTC is V=0.917106 [Cu2+]0.87921 [DBDTC]2.03021. Based on the kinetic data, and formed complex compounds estimation, the mechanism explaining by 2 stages. In the first stage formation of [Cu(DBDTC)], and then [Cu(DBDTC)2] with the last structure geomethry planar rectangle. The result of this research will be more useful if an effort is being done in reaction mechanism by chemical computation method for obtain intermediate, and for constant “k” in same stage, k1.k2. and compound complex constanta (β).

  2. Noise-Induced Modulation of the Relaxation Kinetics around a Non-Equilibrium Steady State of Non-Linear Chemical Reaction Networks

    OpenAIRE

    Ramaswamy, Rajesh; Sbalzarini, Ivo F; González-Segredo, Nélido

    2011-01-01

    Stochastic effects from correlated noise non-trivially modulate the kinetics of non-linear chemical reaction networks. This is especially important in systems where reactions are confined to small volumes and reactants are delivered in bursts. We characterise how the two noise sources confinement and burst modulate the relaxation kinetics of a non-linear reaction network around a non-equilibrium steady state. We find that the lifetimes of species change with burst input and confinement. Confi...

  3. A kinetic model for chemical reactions without barriers: transport coefficients and eigenmodes

    International Nuclear Information System (INIS)

    Alves, Giselle M; Kremer, Gilberto M; Marques, Wilson Jr; Soares, Ana Jacinta

    2011-01-01

    The kinetic model of the Boltzmann equation proposed in the work of Kremer and Soares 2009 for a binary mixture undergoing chemical reactions of symmetric type which occur without activation energy is revisited here, with the aim of investigating in detail the transport properties of the reactive mixture and the influence of the reaction process on the transport coefficients. Accordingly, the non-equilibrium solutions of the Boltzmann equations are determined through an expansion in Sonine polynomials up to the first order, using the Chapman–Enskog method, in a chemical regime for which the reaction process is close to its final equilibrium state. The non-equilibrium deviations are explicitly calculated for what concerns the thermal–diffusion ratio and coefficients of shear viscosity, diffusion and thermal conductivity. The theoretical and formal analysis developed in the present paper is complemented with some numerical simulations performed for different concentrations of reactants and products of the reaction as well as for both exothermic and endothermic chemical processes. The results reveal that chemical reactions without energy barrier can induce an appreciable influence on the transport properties of the mixture. Oppositely to the case of reactions with activation energy, the coefficients of shear viscosity and thermal conductivity become larger than those of an inert mixture when the reactions are exothermic. An application of the non-barrier model and its detailed transport picture are included in this paper, in order to investigate the dynamics of the local perturbations on the constituent number densities, and velocity and temperature of the whole mixture, induced by spontaneous internal fluctuations. It is shown that for the longitudinal disturbances there exist two hydrodynamic sound modes, one purely diffusive hydrodynamic mode and one kinetic mode

  4. A kinetic model for chemical reactions without barriers: transport coefficients and eigenmodes

    Science.gov (United States)

    Alves, Giselle M.; Kremer, Gilberto M.; Marques, Wilson, Jr.; Jacinta Soares, Ana

    2011-03-01

    The kinetic model of the Boltzmann equation proposed in the work of Kremer and Soares 2009 for a binary mixture undergoing chemical reactions of symmetric type which occur without activation energy is revisited here, with the aim of investigating in detail the transport properties of the reactive mixture and the influence of the reaction process on the transport coefficients. Accordingly, the non-equilibrium solutions of the Boltzmann equations are determined through an expansion in Sonine polynomials up to the first order, using the Chapman-Enskog method, in a chemical regime for which the reaction process is close to its final equilibrium state. The non-equilibrium deviations are explicitly calculated for what concerns the thermal-diffusion ratio and coefficients of shear viscosity, diffusion and thermal conductivity. The theoretical and formal analysis developed in the present paper is complemented with some numerical simulations performed for different concentrations of reactants and products of the reaction as well as for both exothermic and endothermic chemical processes. The results reveal that chemical reactions without energy barrier can induce an appreciable influence on the transport properties of the mixture. Oppositely to the case of reactions with activation energy, the coefficients of shear viscosity and thermal conductivity become larger than those of an inert mixture when the reactions are exothermic. An application of the non-barrier model and its detailed transport picture are included in this paper, in order to investigate the dynamics of the local perturbations on the constituent number densities, and velocity and temperature of the whole mixture, induced by spontaneous internal fluctuations. It is shown that for the longitudinal disturbances there exist two hydrodynamic sound modes, one purely diffusive hydrodynamic mode and one kinetic mode.

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

    International Nuclear Information System (INIS)

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

    2007-01-01

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

  6. Pre-steady-state kinetics of Escherichia coli aspartate aminotransferase catalyzed reactions and thermodynamic aspects of its substrate specificity

    International Nuclear Information System (INIS)

    Kuramitsu, Seiki; Hiromi, Keitaro; Hayashi, Hideyuki; Morino, Yoshimasa; Kagamiyama, Hiroyuki

    1990-01-01

    The four half-transamination reactions [the pyridoxal form of Escherichia coli aspartate aminotransferase (AspAT) with aspartate or glutamate and the pyridoxamine form of the enzyme with oxalacetate or 2-oxoglutarate] were followed in a stopped-flow spectrometer by monitoring the absorbance change at either 333 or 358 nm. The reaction progress curves in all cases gave fits to a monophasic exponential process. Kinetic analyses of these reactions showed that each half-reaction is composed of the following three processes: (1) the rapid binding of an amino acid substrate to the pyridoxal form of the enzyme; (2) the rapid binding of the corresponding keto acid to the pyridoxamine form of the enzyme; (3) the rate-determining interconversion between the two complexes. This mechanism was supported by the findings that the equilibrium constants for half- and overall-transamination reactions and the steady-state kinetic constants agreed well with the predicted values on the basis of the above mechanism using pre-steady-state kinetic parameters. The significant primary kinetic isotope effect observed in the reaction with deuterated amino acid suggests that the withdrawal of the α-proton of the substrates is rate determining. The pyridoxal form of E. coli AspAT reacted with a variety of amino acids as substrates. The substrate specificity of the E. coli enzyme was much broader than that of pig isoenzymes, reflecting some subtle but distinct difference in microenvironment accommodating the side chain of the substrate between e. coli and mammalian AspATs

  7. Reaction kinetics of free fatty acids esterification in palm fatty acid distillate using coconut shell biochar sulfonated catalyst

    Science.gov (United States)

    Hidayat, Arif; Rochmadi, Wijaya, Karna; Budiman, Arief

    2015-12-01

    Recently, a new strategy of preparing novel carbon-based solid acids has been developed. In this research, the esterification reactions of Palm Fatty Acid Distillate (PFAD) with methanol, using coconut shell biochar sulfonated catalyst from biomass wastes as catalyst, were studied. In this study, the coconut shell biochar sulfonated catalysts were synthesized by sulfonating the coconut shell biochar using concentrated H2SO4. The kinetics of free fatty acid (FFA) esterification in PFAD using a coconut shell biochar sulfonated catalyst was also studied. The effects of the mass ratio of catalyst to oil (1-10%), the molar ratio of methanol to oil (6:1-12:1), and the reaction temperature (40-60°C) were studied for the conversion of PFAD to optimize the reaction conditions. The results showed that the optimal conditions were an methanol to PFAD molar ratio of 12:1, the amount of catalyst of 10%w, and reaction temperature of 60°C. The proposed kinetic model shows a reversible second order reaction and represents all the experimental data satisfactorily, providing deeper insight into the kinetics of the reaction.

  8. 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

  9. Lattice defects as Lotka-Volterra societies

    Energy Technology Data Exchange (ETDEWEB)

    Yost, F.G.

    1995-07-01

    Since the early part of this century the Lotka-Volterra or predator-prey equations have been known to simulate the stability, instability, and persistent oscillations observed in many biological and ecological societies. These equations have been modified in many ways and have been used to model phenomena as varied as childhood epidemics, enzyme reactions, and conventional warfare. In the work to be described, similarities are drawn between various lattice defects and Lotka-Volterra (LV) societies. Indeed, grain boundaries are known to ``consume`` dislocations, inclusions ``infect`` grain boundaries, and dislocations ``annihilate`` dislocations. Several specific cases of lattice defect interaction kinetics models are drawn from the materials science literature to make these comparisons. Each model will be interpreted as if it were a description of a biological system. Various approaches to the modification of this class of interaction kinetics will be presented and discussed. The earliest example is the Damask-Dienes treatment of vacancy-divacancy annealing kinetics. This historical model will be modified to include the effects of an intermediate species and the results will be compared with the original model. The second example to be examined is the Clark-Alden model for deformation-enhanced grain growth. Dislocation kinetics will be added to this model and results will be discussed considering the original model. The third example to be presented is the Ananthakrishna-Sahoo model of the Portevin-Le Chatelier effect that was offered in 1985 as an extension of the classical Cottrell atmosphere explanation. Their treatment will be modified by inclusion of random interference from a pesky but peripheral species and by allowing a rate constant to be a function of time.

  10. Kinetics of the reaction between H· and superheated water probed with muonium

    Energy Technology Data Exchange (ETDEWEB)

    Alcorn, C. [Mount Allison Univ., Sackville, NB (Canada); Brodovitch, J.-C. [Simon Fraser Univ., Burnaby, BC (Canada); Ghandi, K.; Kennedy, A. [Mount Allison Univ., Sackville, NB (Canada); Percival, P.W. [Simon Fraser Univ., Burnaby, BC (Canada); TRIUMF, Vancouver, BC (Canada); Smith, M. [Mount Allison Univ., Sackville, NB (Canada)

    2011-07-01

    Safe operation of a supercritical water cooled reactor requires knowledge of the reaction kinetics of transient species formed by the radiolysis of water in the temperature range 300-650{sup o}C. By using a light isotope of the H·atom, it is possible to study its chemistry in water over this range of temperatures. Arguably, the most important reaction to study is that of the H·atom with the bulk solvent. This reaction could provide an in situ source of H{sub 2} gas, which is added to CANDU reactors to suppress oxidative corrosion. The work described here concerns studies of the reaction of muonium with H{sub 2}O and D{sub 2}O at temperatures up to 450{sup o}C.

  11. Thermo-kinetic mechanisms for grain boundary structure multiplicity, thermal instability and defect interactions

    International Nuclear Information System (INIS)

    Burbery, N.J.; Das, R.; Ferguson, W.G.

    2016-01-01

    Grain boundaries (GBs) provide a source and/or a sink for crystal defects and store elastic energy due to the non-uniform atomic bonding structure of the GB core. GB structures are thermodynamically driven to transition to the lowest energy configuration possible; however to date there has been little evidence to explain why specific GB structures have a low energy state. Furthermore, there is little quantitative demonstration of the significance of physical and GB structure characteristics on the GB energy, thermal stability, and the effect of temporary local GB structure transformations on defect interactions. This paper evaluates the defect interactions and structure stability of multiple Σ5(310) GB structures in bi-crystals of pure aluminium, and systematically investigates the features at 0 K to characterise multiple metastable structures. Structure stability is evaluated by utilising unstable vacancy defects to initiate GB transformations, and using nudged elastic band simulations to quantify this with the activation energy. The emission of stable vacancy defects from the ‘stable’ and metastable grain boundaries is also evaluated in the same manner. A detailed analysis of dislocation nucleation at the atomistic scale demonstrates that local transformations of GB structure between stable and metastable intermediates can provide a mechanism to accommodate the generation of crystal defects. Kinetic (time-dependent) effects that compete with energetic driving forces for structural transformations of GBs are shown to cause a significant effect on the activation properties that may exceed the influence of GB potential energy. The results demonstrate that GB structural multiplicity can be associated with the generation and absorption of dislocations and vacancies. This paper demonstrates the suitability of atomistic simulations coupled with nudged elastic band simulations to evaluate fundamental thermodynamic properties of pure FCC metals. Overall, this paper

  12. Thermo-kinetic mechanisms for grain boundary structure multiplicity, thermal instability and defect interactions

    Energy Technology Data Exchange (ETDEWEB)

    Burbery, N.J. [Department of Mechanical Engineering, University of Auckland, Auckland 1010 (New Zealand); Das, R., E-mail: r.das@auckland.ac.nz [Department of Mechanical Engineering, University of Auckland, Auckland 1010 (New Zealand); Ferguson, W.G. [Department of Chemical and Materials Engineering, University of Auckland, Auckland 1010 (New Zealand)

    2016-08-15

    Grain boundaries (GBs) provide a source and/or a sink for crystal defects and store elastic energy due to the non-uniform atomic bonding structure of the GB core. GB structures are thermodynamically driven to transition to the lowest energy configuration possible; however to date there has been little evidence to explain why specific GB structures have a low energy state. Furthermore, there is little quantitative demonstration of the significance of physical and GB structure characteristics on the GB energy, thermal stability, and the effect of temporary local GB structure transformations on defect interactions. This paper evaluates the defect interactions and structure stability of multiple Σ5(310) GB structures in bi-crystals of pure aluminium, and systematically investigates the features at 0 K to characterise multiple metastable structures. Structure stability is evaluated by utilising unstable vacancy defects to initiate GB transformations, and using nudged elastic band simulations to quantify this with the activation energy. The emission of stable vacancy defects from the ‘stable’ and metastable grain boundaries is also evaluated in the same manner. A detailed analysis of dislocation nucleation at the atomistic scale demonstrates that local transformations of GB structure between stable and metastable intermediates can provide a mechanism to accommodate the generation of crystal defects. Kinetic (time-dependent) effects that compete with energetic driving forces for structural transformations of GBs are shown to cause a significant effect on the activation properties that may exceed the influence of GB potential energy. The results demonstrate that GB structural multiplicity can be associated with the generation and absorption of dislocations and vacancies. This paper demonstrates the suitability of atomistic simulations coupled with nudged elastic band simulations to evaluate fundamental thermodynamic properties of pure FCC metals. Overall, this paper

  13. A Detailed Chemical Kinetic Reaction Mechanism for Oxidation of Four Small Alkyl Esters in Laminar Premixed Flames

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C K; Pitz, W J; Westmoreland, P R; Dryer, F L; Chaos, M; Osswald, P; Kohse-Hoinghaus, K; Cool, T A; Wang, J; Yang, B; Hansen, N; Kasper, T

    2008-02-08

    A detailed chemical kinetic reaction mechanism has been developed for a group of four small alkyl ester fuels, consisting of methyl formate, methyl acetate, ethyl formate and ethyl acetate. This mechanism is validated by comparisons between computed results and recently measured intermediate species mole fractions in fuel-rich, low pressure, premixed laminar flames. The model development employs a principle of similarity of functional groups in constraining the H atom abstraction and unimolecular decomposition reactions in each of these fuels. As a result, the reaction mechanism and formalism for mechanism development are suitable for extension to larger oxygenated hydrocarbon fuels, together with an improved kinetic understanding of the structure and chemical kinetics of alkyl ester fuels that can be extended to biodiesel fuels. Variations in concentrations of intermediate species levels in these flames are traced to differences in the molecular structure of the fuel molecules.

  14. Study of kinetics and mechanism of diazo compound reactions using nuclear chemical polarization

    International Nuclear Information System (INIS)

    Gragerov, I.P.; Levit, A.F.; Kiprianova, L.A.; Buchachenko, A.L.; Sterleva, T.G.

    1975-01-01

    It has been established that at the rate-determining steps of the radical reactions in which aniline interacts with isoamyl nitrite and substituted diazo salts interact with sodium methylate, tertiary fatty amines, or phosphinic acid, no transfer of a single electron occurs. The processes of single electron transfer do not seem to play a decisive role in the kinetics of most transformations of diazo compounds. Chemical nuclear polarization is shown to be suitable for kinetic studies of fast radical processes

  15. Reaction of diazepam and related benzodiazepines with chlorine. Kinetics, transformation products and in-silico toxicological assessment.

    Science.gov (United States)

    Carpinteiro, Inmaculada; Rodil, Rosario; Quintana, José Benito; Cela, Rafael

    2017-09-01

    In this work, the reaction of four benzodiazepines (diazepam, oxazepam, nordazepam and temazepam) during water chlorination was studied by means of liquid chromatography-quadrupole-time of flight-mass spectrometry (LC-QTOF-MS). For those compounds that showed a significant degradation, i.e. diazepam, oxazepam and nordazepam, parameters affecting to the reaction kinetics (pH, chlorine and bromide level) were studied in detail and transformation products were tentatively identified. The oxidation reactions followed pseudofirst-order kinetics with rate constants in the range of 1.8-42.5 M -1  s -1 , 0.13-1.16 M -1  s -1 and 0.04-20.4 M -1  s -1 corresponding to half-life values in the range of 1.9-146 min, 1.8-87 h and 2.5-637 h for oxazepam, nordazepam and diazepam, respectively, depending of the levels of studied parameters. Chlorine and pH affected significantly the reaction kinetics, where an increase of the pH resulted into a decrease of the reaction rate, whereas higher chlorine dosages led to faster kinetics, as expected in this case. The transformation of the studied benzodiazepines occurs mainly at the 1,4-diazepine 7-membered-ring, resulting in ring opening to form benzophenone derivatives or the formation of a 6-membered pyrimidine ring, leading to quinazoline derivatives. The formation of these by-products was also tested in real surface water samples observing kinetics of oxazepam degradation slower in river than in creek water, while the degradation of the two other benzodiazepines occurred only in the simpler sample (creek water). Finally, the acute and chronical toxicity and mutagenicity of precursors and transformation products were estimated using quantitative structure-activity relationship (QSAR) software tools: Ecological Structure Activity Relationships (ECOSAR) and Toxicity Estimation Software Tool (TEST), finding that some transformation products could be more toxic/mutagenic than the precursor drug, but additional test would be needed

  16. Aspartate aminotransferase: the kinetic barriers facing the covalent intermediates on the reaction pathway

    International Nuclear Information System (INIS)

    Kirsch, J.F.; Julin, D.A.; McLeish, M.; Wiesinger, H.

    1986-01-01

    The intermediates, aldimine (A), quinonoid (Q) and ketimine (K), along the transaminase reaction coordinate were probed by isotope transfer and solvent exchange kinetics. Less than 0.003% of 3 H is transferred from C/sub α/[ 3 H]-aspartate to pyridoxamine phosphate in the cytoplasmic aspartate aminotransferase (cAATase) reaction implying either that Q does not exist as a kinetically competent intermediate or that there is a rapid exchange of isotope with solvent. The ratio of the rate constants for C/sub α/ hydrogen exchange vs keto acid product formation (k/sub exge//k/sub prod/) are 2.5 and 0.5 for the reactions of cAATase with C/sub α/ [ 2 H]-aspartate and mitochondrial (m) AATase with C/sub α/[ 2 H]-glutamate respectively. The latter reaction was also probed from the α-keto-glutarate side with carbonyl 0-18 enriched keto acid. This experiment gave k/sub exge//k/sub prod/ = 1.0 for oxygen-18 exchange in α-ketoglutarate versus amino acid formation. The two exchange experiments with mAATase are interpreted in terms of a model in which the rate constant for diffusion of water from the active site is comparable with those for product forming steps

  17. Kinetic calorimetry in the study of the mechanism of low-temperature chemical reactions

    Science.gov (United States)

    Barkalov, I. M.; Kiryukhin, D. P.

    Chemical reactions are always followed by a change in the reacting system enthalpy, hence, calorimetry as a method of enthalpy and heat capacity measuring is a universal and, sometimes, even the only possible way of studying chemical reaction kinetics. Throughout its long history, the calorimeter, having preserved the positions of the main method of thermodynamic studies, has conquered a new field of application: that of kinetic study of chemical reactions. The advantages and disadvantages of the kinetic calorimeter are now obvious. First, the advantages are: (1) the possibility of measuring the rate of a chemical reaction without any special requirements being imposed on the reaction medium (solid, viscous, multicomponent systems); (2) the high efficiency: a large volume of kinetic information in one experiment and a non-destructive character of changes; (3) the possibility of measuring directly in the field of ionizing radiation (γ-radiation, accelerated electrons) and light; and (4) recording of the chemical conversion directly at the time of its occurrence. The disadvantages of this method are: (1) the high inertia of standard calorimeter systems (τC⋍102-103S), which restricts the possibilities of studying fast processes; and (2) the complexity of the correct organization of the calorimeter experiment when the parameters of the process are changed (overheating in the sample, conversion of the process to explosive and auto wave regimens). One of the oldest and most universal methods of studying the mechanism of chemical reactions, calorimetry, is now passing through a period of turbulent development due to the advances in electronics and computerization. The wide variety of types of calorimeter set-ups and the large assortment of measurement schemes in the currently described methods complicate the experimental selection of the necessary instrument rather than facilitate it. The basic principles of the method, the types of calorimeters, and the measuring

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

    National Research Council Canada - National Science Library

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

    2000-01-01

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

  19. Using ground reaction force to predict knee kinetic asymmetry following anterior cruciate ligament reconstruction.

    Science.gov (United States)

    Dai, B; Butler, R J; Garrett, W E; Queen, R M

    2014-12-01

    Asymmetries in sagittal plane knee kinetics have been identified as a risk factor for anterior cruciate ligament (ACL) re-injury. Clinical tools are needed to identify the asymmetries. This study examined the relationships between knee kinetic asymmetries and ground reaction force (GRF) asymmetries during athletic tasks in adolescent patients following ACL reconstruction (ACL-R). Kinematic and GRF data were collected during a stop-jump task and a side-cutting task for 23 patients. Asymmetry indices between the surgical and non-surgical limbs were calculated for GRF and knee kinetic variables. For the stop-jump task, knee kinetics asymmetry indices were correlated with all GRF asymmetry indices (P kinetic asymmetry indices were correlated with the peak propulsion vertical GRF and vertical GRF impulse asymmetry indices (P kinetic asymmetries and therefore may assist in optimizing rehabilitation outcomes and minimizing re-injury rates. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

  20. Kinetics of liquid lithium reaction with oxygen-nitrogen mixtures

    International Nuclear Information System (INIS)

    Gil, T.K.; Kazimi, M.S.

    1986-01-01

    A series of experiments have been conducted in order to characterize the kinetics of lithium chemical reaction with a mixture of oxygen and nitrogen. Three mixed gas compositions were used; 80% N 2 and 20% O 2 , 90% N 2 and 10% O 2 , and 95% N 2 and 5% O 2 . The reaction rate was obtained as a function of lithium temperature and the oxygen fraction. Liquid lithium temperature varied from 400 to 1100 0 C. By varying the composition, the degree of inhibition of the lithium-nitrogen reaction rate due to the presence of oxygen was observed. The results indicate that the lithium-nitrogen reaction rate depended on both the fraction of oxygen present and lithium temperature. The lithium nitride layer formed from the reaction also had a significant inhibition effect on the lithium-nitrogen reaction rate while the lithium-oxygen reaction rate was not as greatly hindered. LITFIRE, a computer code which simulates temperature and pressure history in a containment building following lithium spills, was modified by including (1) an improved model for the lithium-nitrogen reaction rate and (2) a model for the lithium-CO 2 reaction. LITFIRE was used to simulate HEDL's LC-2 and LA-5 experiments, and the predicted temperatures and pressures were in a reasonable agreement. Furthermore, LITFIRE was applied to a prototypical fusion reactor containment in order to simulate the consequences of a lithium spill accident. The result indicated that if nitrogen was used as containment building gas during the accident, the consequences of the accident would be less severe than those with air. The pressure rise in the building was found to be reduced by 50% and the maximum temperature of the combustion zone was limited to 900 0 C instead of 1200 0 C in the case of air

  1. A kinetic-theory approach for computing chemical-reaction rates in upper-atmosphere hypersonic flows.

    Science.gov (United States)

    Gallis, Michael A; Bond, Ryan B; Torczynski, John R

    2009-09-28

    Recently proposed molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction-rate information) are investigated for chemical reactions occurring in upper-atmosphere hypersonic flows. The new models are in good agreement with the measured Arrhenius rates for near-equilibrium conditions and with both measured rates and other theoretical models for far-from-equilibrium conditions. Additionally, the new models are applied to representative combustion and ionization reactions and are in good agreement with available measurements and theoretical models. Thus, molecular-level chemistry modeling provides an accurate method for predicting equilibrium and nonequilibrium chemical-reaction rates in gases.

  2. X-ray analysis of temperature induced defect structures in boron implanted silicon

    Science.gov (United States)

    Sztucki, M.; Metzger, T. H.; Kegel, I.; Tilke, A.; Rouvière, J. L.; Lübbert, D.; Arthur, J.; Patel, J. R.

    2002-10-01

    We demonstrate the application of surface sensitive diffuse x-ray scattering under the condition of grazing incidence and exit angles to investigate growth and dissolution of near-surface defects after boron implantation in silicon(001) and annealing. Silicon wafers were implanted with a boron dose of 6×1015 ions/cm2 at 32 keV and went through different annealing treatments. From the diffuse intensity close to the (220) surface Bragg peak we reveal the nature and kinetic behavior of the implantation induced defects. Analyzing the q dependence of the diffuse scattering, we are able to distinguish between point defect clusters and extrinsic stacking faults on {111} planes. Characteristic for stacking faults are diffuse x-ray intensity streaks along directions, which allow for the determination of their growth and dissolution kinetics. For the annealing conditions of our crystals, we conclude that the kinetics of growth can be described by an Ostwald ripening model in which smaller faults shrink at the expense of the larger stacking faults. The growth is found to be limited by the self-diffusion of silicon interstitials. After longer rapid thermal annealing the stacking faults disappear almost completely without shrinking, most likely by transformation into perfect loops via a dislocation reaction. This model is confirmed by complementary cross-sectional transmission electron microscopy.

  3. 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

  4. Thermodynamic and kinetic analysis of the reaction between biological catecholamines and chlorinated methylperoxy radicals

    Science.gov (United States)

    Dimić, Dušan S.; Milenković, Dejan A.; Marković, Jasmina M. Dimitrić; Marković, Zoran S.

    2018-05-01

    The antiradical potency of catecholamines (dopamine, epinephrine, norepinephrine, L-DOPA), metabolites of dopamine (homovanillic acid, 3-methoxytyramine and 3,4-dihydroxyphenylacetic acid) and catechol towards substituted methylperoxy radicals is investigated. The thermodynamic parameters, together with the kinetic approach, are used to determine the most probable mechanism of action. The natural bond orbital and quantum theory of atoms in molecules are utilised to explain the highest reactivity of trichloromethylperoxy radical. The preferred mechanism is dependent both on the thermodynamic and kinetic parameters . The number of chlorine atoms on radical, the presence of intra-molecular hydrogen bond and number of hydroxy groups attached to the aromatic ring significantly influence the mechanism. The results suggest that sequential proton loss electron transfer (SPLET) is the most probable for reaction with methylperoxy and hydrogen atom transfer (HAT) for reaction with trichloromethylperoxy radicals, with a gradual transition between SPLET and HAT for other two radicals. Due to the significant deprotonation of molecules containing the carboxyl group, the respective anions are also investigated. The HAT and SPLET mechanisms are highly competitive in reaction with MP radical, while the dominant mechanism towards chlorinated radicals is HAT. The reactions in methanol and benzene are also discussed.

  5. On an aspect of kinetics both defects accumulation and gas absorption in an irradiated metals oxides

    International Nuclear Information System (INIS)

    Tuseev, T.; Polyakov, A.I.; Bitenbaev, M.I.

    2001-01-01

    In the work an analysis of experimental data during study both gases adsorption processes and radiation defects accumulation in irradiated (ultraviolet, gamma-, neutron-, alpha-particle- and proton radiation) in the oxides (SiO 2 , Al 2 O 3 , BeO, Se 2 O 3 , Dy 2 O 3 , La 2 O 3 , Er 2 O 3 ) is carried out. It is determined, that these processes are correlating with each other and equivalent kinetic equations for its description are proposed

  6. Quantitative modeling of the reaction/diffusion kinetics of two-chemistry photopolymers

    Science.gov (United States)

    Kowalski, Benjamin Andrew

    Optically driven diffusion in photopolymers is an appealing material platform for a broad range of applications, in which the recorded refractive index patterns serve either as images (e.g. data storage, display holography) or as optical elements (e.g. custom GRIN components, integrated optical devices). A quantitative understanding of the reaction/diffusion kinetics is difficult to obtain directly, but is nevertheless necessary in order to fully exploit the wide array of design freedoms in these materials. A general strategy for characterizing these kinetics is proposed, in which key processes are decoupled and independently measured. This strategy enables prediction of a material's potential refractive index change, solely on the basis of its chemical components. The degree to which a material does not reach this potential reveals the fraction of monomer that has participated in unwanted reactions, reducing spatial resolution and dynamic range. This approach is demonstrated for a model material similar to commercial media, achieving quantitative predictions of index response over three orders of exposure dose (~1 to ~103 mJ cm-2) and three orders of feature size (0.35 to 500 microns). The resulting insights enable guided, rational design of new material formulations with demonstrated performance improvement.

  7. Kinetics and Mechanism of the Reaction of Hydoxyl Radicals with Acetonitrile under Atmospheric Conditions

    Science.gov (United States)

    Hynes, A. J.; Wine, P. H.

    1997-01-01

    The pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to determine absolute rate coefficients for the reaction OH + CH3CN (1) and its isotopic variants, OH + CD3CN (2), OD + CH3CN (3), and OD + CD3CN (4). Reactions 1 and 2 were studied as a function of pressure and temperature in N2, N2/O2, and He buffer gases. In the absence of O2 all four reactions displayed well-behaved kinetics with exponential OH decays and pseudo-first rate constants which were proportional to substrate concentration. Data obtained in N2 over the range 50-700 Torr at 298 K are consistent with k(sub 1), showing a small pressure dependence. The Arrhenius expression obtained by averaging data at all pressures in k(sub 1)(T) = (1.1(sup +0.5)/(sub -0.3)) x 10(exp -12) exp[(-1130 +/- 90)/T] cu cm /(molecule s). The kinetics of reaction 2 are found to be pressure dependent with k(sub 2) (298 K) increasing from (1.21 +/- 0.12) x 10(exp -14) to (2.16 +/- 0.11) x 10(exp -14) cm(exp 3)/ (molecule s) over the pressure range 50-700 Torr of N2 at 298 K. Data at pressures greater than 600 Torr give k(sub 2)(T) = (9.4((sup +13.4)(sub -5.0))) x 10(exp -13) exp[(-1180 +/- 250)/T] cu cm/(molecule s). The rates of reactions 3 and 4 are found to be independent of pressure over the range 50-700 Torr of N2 with 298 K rate coefficient given by k(sub 3) =(3.18 +/- 0.40) x 10(exp -14) cu cm/(molecule s) and k(sub 4) = (2.25 +/-0.28) x 10(exp -14) cu cm/(molecule s). In the presence of O2 each reaction shows complex (non-pseudo-first-order) kinetic behavior and/or an apparent decrease in the observed rate constant with increasing [O2], indicating the presence of significant OH or OD regeneration. Observation of regeneration of OH in (2) and OD in (3) is indicative of a reaction channel which proceeds via addition followed by reaction of the adduct, or one of its decomposition products, with O2. The observed OH and OD decay profiles have been modeled by using a simple mechanistic

  8. alfa-Deuterium kinetic isotope effects in reactions of methyllithium. Is better aggregation the cause of lower reactivity?

    DEFF Research Database (Denmark)

    Holm, Torkil

    1996-01-01

    The value of kH/kD for alfa deuterium kinetic isotope effects for the reaction of methyllithium and methylmagnesium iodid with a series of substrates are consistently ca. 10-15 % higher for the lithium reagent. This may indicate a pre-equilibrium......The value of kH/kD for alfa deuterium kinetic isotope effects for the reaction of methyllithium and methylmagnesium iodid with a series of substrates are consistently ca. 10-15 % higher for the lithium reagent. This may indicate a pre-equilibrium...

  9. 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.

  10. Nucleation and growth kinetics for intercalated islands during deposition on layered materials with isolated pointlike surface defects

    International Nuclear Information System (INIS)

    Han, Yong; Lii-Rosales, A.; Zhou, Y.; Wang, C.-J.

    2017-01-01

    Theory and stochastic lattice-gas modeling is developed for the formation of intercalated metal islands in the gallery between the top layer and the underlying layer at the surface of layered materials. Our model for this process involves deposition of atoms, some fraction of which then enter the gallery through well-separated pointlike defects in the top layer. Subsequently, these atoms diffuse within the subsurface gallery leading to nucleation and growth of intercalated islands nearby the defect point source. For the case of a single point defect, continuum diffusion equation analysis provides insight into the nucleation kinetics. However, complementary tailored lattice-gas modeling produces a more comprehensive and quantitative characterization. We analyze the large spread in nucleation times and positions relative to the defect for the first nucleated island. We also consider the formation of subsequent islands and the evolution of island growth shapes. The shapes reflect in part our natural adoption of a hexagonal close-packed island structure. As a result, motivation and support for the model is provided by scanning tunneling microscopy observations of the formation of intercalated metal islands in highly-ordered pyrolytic graphite at higher temperatures.

  11. Kinetics and mechanisms of the reactions of alkyl radicals with oxygen and with complexes of Co(III), Ru(III), and Ni(III)

    International Nuclear Information System (INIS)

    Kelley, D.

    1990-01-01

    The kinetics of the reactions of C 2 H 5 radical with Co(NH 3 ) 5 X 2+ , Ru(NH 3 ) 5 X 2+ , and Co(dmgH) 2 (X) (Y) (X = Br, Cl, N 3 , SCN; Y = H 2 O, CH 3 CN) complexes were studied using laser flash photolysis of ethylcobalt complexes. The kinetics were obtained by the kinetic probe method. Some relative rate constants were also determined by a competition method based on ethyl halide product ratios. The kinetics of colligation reactions of a series of alkyl radicals with β-Ni(cyclam) 2+ were studied using flaser flash photolysis of alkylcobalt complexes. Again, the kinetics were obtained by employing the kinetic probe competition method. The kinetics of the unimolecular homolysis of a series of RNi(cyclam)H 2 O 2+ were studied. Activation parameters were obtained for the unimolecular homolysis of C 2 H 5 Ni(cyclam)H 2 O 2+ . Kinetic and thermodynamic data obtained from these reactions were compared with those for the σ-bonded organometallic complexes. The kinetics of the unimolecular homolysis of a series of RNi(cyclam)H 2 O 2+ complexes were studied by monitoring the formation of the oxygen insertion product RO 2 Ni(cyclam)H 2 O 2+ . The higher rate constants for the reactions of alkyl radicals with oxygen in solution, as compared with those measured in the gas phase, were discussed. 30 refs

  12. Defect clustering in concentrated alloys during irradiation

    International Nuclear Information System (INIS)

    Hashimoto, T.; Shigenaka, N.; Fuse, M.

    1992-01-01

    A rate theory based model is presented to investigate the kinetics of interstitial clustering processes in a face-centered cubic (fcc) binary alloy containing A- and B-atoms. Three types of interstitial dumbbells, AA-, BB- and AB-type dumbbells, are considered. Conversions between these interstitial dumbbells are explicitly introduced into the formulation, based on the consideration of dumbbell configurations and movements. A di- interstitial is assumed to be the nucleus of a dislocation loop. Reactions of point defect production by irradiation, mutual recombination of an interstitial and a vacancy, dislocation loop nucleation and their growth are included in the model. Parameter values are chosen based on the atom size of the alloy elements, and dislocation loop formation kinetics are investigated while varying alloy compositions. Two different types of kinetics are obtained in accordance with the dominant loop nucleus types. Conversions between interstitial dumbbells are important in the determination of the interstitial dumbbell concentration ratios, of the dominant nucleus types, and consequently, the loop formation kinetics. Dislocation loop concentration decreases with increasing undersized atom content, but dose rate and temperature dependence of loop concentration are insensitive to alloy compositions. (author)

  13. 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

  14. On the ultrafast kinetics of the energy and electron transfer reactions in photosystem I

    Energy Technology Data Exchange (ETDEWEB)

    Slavov, Chavdar Lyubomirov

    2009-07-09

    The subject of the current work is one of the main participants in the light-dependent phase of oxygenic photosynthesis, Photosystem I (PS I). This complex carries an immense number of cofactors: chlorophylls (Chl), carotenoids, quinones, etc, which together with the protein entity exhibit several exceptional properties. First, PS I has an ultrafast light energy trapping kinetics with a nearly 100% quantum efficiency. Secondly, both of the electron transfer branches in the reaction center are suggested to be active. Thirdly, there are some so called 'red' Chls in the antenna system of PS I, absorbing light with longer wavelengths than the reaction center. These 'red' Chls significantly modify the trapping kinetics of PS I. The purpose of this thesis is to obtain better understanding of the above-mentioned, specific features of PS I. This will not merely cast more light on the mechanisms of energy and electron transfer in the complex, but also will contribute to the future developments of optimized artificial light-harvesting systems. In the current work, a number of PS I complexes isolated from different organisms (Thermosynechococcus elongatus, Chlamydomonas reinhardtii, Arabidopsis thaliana) and possessing distinctive features (different macroorganisation, monomers, trimers, monomers with a semibelt of peripheral antenna attached; presence of 'red' Chls) is investigated. The studies are primarily focused on the electron transfer kinetics in each of the cofactor branches in the PS I reaction center, as well as on the effect of the antenna size and the presence of 'red' Chls on the trapping kinetics of PS I. These aspects are explored with the help of several ultrafast optical spectroscopy methods: (i) time-resolved fluorescence ? single photon counting and synchroscan streak camera; and (ii) ultrafast transient absorption. Physically meaningful information about the molecular mechanisms of the energy trapping in PS I is

  15. Kinetic isotope effect in the reaction of dehydration of fructose into 5-hydroxymethylfurfural

    International Nuclear Information System (INIS)

    Grin', S.A.; Tsimbaliev, S.R.; Gel'fand, S.Yu.

    1993-01-01

    Kinetic isotopic effect in the reaction of fructose dehydration into 5- hydroxymethylfurfural was determined. The results suggest hydrogen participation in the limiting stage of the process. The assumption that proton addition to 4, 5, 6 -trihydroxy - 2- on - hexal is the limiting stage is made

  16. The renneting of milk : a kinetic study of the enzymic and aggregation reactions

    NARCIS (Netherlands)

    Hooydonk, van A.C.M.

    1987-01-01

    The rennet-induced clotting of milk was studied under various conditions. The kinetics of the enzymic and aggregation reactions was analysed separately and, where possible, related to the physico-chemical properties of the casein micelle and its environment.

    The effects of important

  17. Modelling and simulation of a transketolase mediated reaction: Sensitivity analysis of kinetic parameters

    DEFF Research Database (Denmark)

    Sayar, N.A.; Chen, B.H.; Lye, G.J.

    2009-01-01

    In this paper we have used a proposed mathematical model, describing the carbon-carbon bond format ion reaction between beta-hydroxypyruvate and glycolaldehyde to synthesise L-erythrulose, catalysed by the enzyme transketolase, for the analysis of the sensitivity of the process to its kinetic...

  18. General theory of the multistage geminate reactions of the isolated pairs of reactants. II. Detailed balance and universal asymptotes of kinetics.

    Science.gov (United States)

    Kipriyanov, Alexey A; Doktorov, Alexander B

    2014-10-14

    The analysis of general (matrix) kinetic equations for the mean survival probabilities of any of the species in a sample (or mean concentrations) has been made for a wide class of the multistage geminate reactions of the isolated pairs. These kinetic equations (obtained in the frame of the kinetic approach based on the concept of "effective" particles in Paper I) take into account various possible elementary reactions (stages of a multistage reaction) excluding monomolecular, but including physical and chemical processes of the change in internal quantum states carried out with the isolated pairs of reactants (or isolated reactants). The general basic principles of total and detailed balance have been established. The behavior of the reacting system has been considered on macroscopic time scales, and the universal long-term kinetics has been determined.

  19. Controlling defects and secondary phases of CZTS by surfactant Potassium

    Science.gov (United States)

    Zhu, Junyi; Zhang, Yiou; Tse, Kinfai; Xiao, Xudong

    Cu2ZnSnS4 (CZTS) is a promising photovoltaic absorber material with earth abundant and nontoxic elements. However, the detrimental native defects and secondary phases of CSTS will largely reduce the energy conversion efficiencies. To understand the origin of these problems during the growth of CZTS, we investigated the kinetic processes on CZTS (-1-1-2) surface, using first principles calculations. A surface Zn atom was found to occupy the subsurface Cu site easily due to a low reaction barrier, which may lead to a high ZnCu concentration and a secondary phase of ZnS. These n-type defects may create deep electron traps near the interface and become detrimental to device performance. To reduce the population of ZnCu and the secondary phase, we propose to use K as a surfactant to alter surface kinetic processes. Improvements on crystal quality and device performance based on this surfactant are consistent with early experimental observations. Computing resources were provided by the High Performance Cluster Computing Centre, Hong Kong Baptist University. This work was supported by the start-up funding at CUHK.

  20. Reaction kinetics in open reactors and serial transfers between closed reactors

    Science.gov (United States)

    Blokhuis, Alex; Lacoste, David; Gaspard, Pierre

    2018-04-01

    Kinetic theory and thermodynamics of reaction networks are extended to the out-of-equilibrium dynamics of continuous-flow stirred tank reactors (CSTR) and serial transfers. On the basis of their stoichiometry matrix, the conservation laws and the cycles of the network are determined for both dynamics. It is shown that the CSTR and serial transfer dynamics are equivalent in the limit where the time interval between the transfers tends to zero proportionally to the ratio of the fractions of fresh to transferred solutions. These results are illustrated with a finite cross-catalytic reaction network and an infinite reaction network describing mass exchange between polymers. Serial transfer dynamics is typically used in molecular evolution experiments in the context of research on the origins of life. The present study is shedding a new light on the role played by serial transfer parameters in these experiments.

  1. The influence of gas–solid reaction kinetics in models of thermochemical heat storage under monotonic and cyclic loading

    International Nuclear Information System (INIS)

    Nagel, T.; Shao, H.; Roßkopf, C.; Linder, M.; Wörner, A.; Kolditz, O.

    2014-01-01

    Highlights: • Detailed analysis of cyclic and monotonic loading of thermochemical heat stores. • Fully coupled reactive heat and mass transport. • Reaction kinetics can be simplified in systems limited by heat transport. • Operating lines valid during monotonic and cyclic loading. • Local integral degree of conversion to capture heterogeneous material usage. - Abstract: Thermochemical reactions can be employed in heat storage devices. The choice of suitable reactive material pairs involves a thorough kinetic characterisation by, e.g., extensive thermogravimetric measurements. Before testing a material on a reactor level, simulations with models based on the Theory of Porous Media can be used to establish its suitability. The extent to which the accuracy of the kinetic model influences the results of such simulations is unknown yet fundamental to the validity of simulations based on chemical models of differing complexity. In this article we therefore compared simulation results on the reactor level based on an advanced kinetic characterisation of a calcium oxide/hydroxide system to those obtained by a simplified kinetic model. Since energy storage is often used for short term load buffering, the internal reactor behaviour is analysed under cyclic partial loading and unloading in addition to full monotonic charge/discharge operation. It was found that the predictions by both models were very similar qualitatively and quantitatively in terms of thermal power characteristics, conversion profiles, temperature output, reaction duration and pumping powers. Major differences were, however, observed for the reaction rate profiles themselves. We conclude that for systems not limited by kinetics the simplified model seems sufficient to estimate the reactor behaviour. The degree of material usage within the reactor was further shown to strongly vary under cyclic loading conditions and should be considered when designing systems for certain operating regimes

  2. HYDROBIOGEOCHEM: A coupled model of HYDROlogic transport and mixed BIOGEOCHEMical kinetic/equilibrium reactions in saturated-unsaturated media

    Energy Technology Data Exchange (ETDEWEB)

    Yeh, G.T.; Salvage, K.M. [Pennsylvania State Univ., University Park, PA (United States). Dept. of Civil and Environmental Engineering; Gwo, J.P. [Oak Ridge National Lab., TN (United States); Zachara, J.M.; Szecsody, J.E. [Pacific Northwest National Lab., Richland, WA (United States)

    1998-07-01

    The computer program HYDROBIOGEOCHEM is a coupled model of HYDROlogic transport and BIOGEOCHEMical kinetic and/or equilibrium reactions in saturated/unsaturated media. HYDROBIOGEOCHEM iteratively solves the two-dimensional transport equations and the ordinary differential and algebraic equations of mixed biogeochemical reactions. The transport equations are solved for all aqueous chemical components and kinetically controlled aqueous species. HYDROBIOGEOCHEM is designed for generic application to reactive transport problems affected by both microbiological and geochemical reactions in subsurface media. Input to the program includes the geometry of the system, the spatial distribution of finite elements and nodes, the properties of the media, the potential chemical and microbial reactions, and the initial and boundary conditions. Output includes the spatial distribution of chemical and microbial concentrations as a function of time and space, and the chemical speciation at user-specified nodes.

  3. THEORETICAL RESEARCH ON THE MULTI-CHANNEL REACTION MECHANISM AND KINETICS OF HNCS WITH OH-

    Directory of Open Access Journals (Sweden)

    Li-Jie Hou

    Full Text Available We presented a theoretical study on the detailed reaction mechanism and kinetics of the HNCS molecule with the OH-. The barrierless minimum energy path and the most favorable entrance channel have been determined by study the thermodynamic and kinetic characters of the channel with low energy barrier. The B3LYP/6-311++G** method was employed for all the geometrical optimizations and a multi-level extrapolation method based on the G3 energies was employed for further energy refinements. In addition, the analysis of the combining interaction between hydroxide ion and HNCS was performed by natural bond orbitals (NBO analysis. The calculation results indicated that the reaction of OH- with HNCS had four channels, and the channel of H-atom in HNCS direct extraction to OH- (OH-+HNCS→IM1→TS3→IM4→P2(SCN- +H2O in singlet state was the main channel with the low potential energy and high equilibrium constant and reaction rate constant. SCN- and H2O were main products.

  4. Kinetic study of the reaction of uranium with various carbon-containing gases

    International Nuclear Information System (INIS)

    Feron, G.

    1963-09-01

    The kinetic study of the reaction U + CO 2 and U + CO has been performed by a thermogravimetric method on a spherical uranium powder, in temperature ranges respectively from 460 to 690 deg. C and from 570 to 850 deg. C. The reaction with carbon dioxide leads to uranium dioxide. A carbon deposition takes place at the same time. The global reactions is the result of two reactions: U + 2 CO 2 → UO 2 + 2 CO U + CO 2 → UO 2 + C The reaction with carbon monoxide leads to a mixture of dioxide UO 2 , dicarbide UC 2 and free carbon. The main reaction can be written. U + CO → 1/2 UO 2 + 1/2 UC 2 The free carbon results of the disproportionation of the carbon monoxide. A remarkable separation of the two phases UO 2 and UC 2 can be observed. A mechanism accounting for the phenomenon has been proposed. The two reactions U + CO 2 and U + CO begin with a long germination period, after which, the reaction velocity seems to be limited in both cases by the ionic diffusion of oxygen through the uranium dioxide. (author) [fr

  5. Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

    International Nuclear Information System (INIS)

    Jorge, Nelly Lidia; Romero, Jorge Marcelo; Grand, André; Hernández-Laguna, Alfonso

    2012-01-01

    Highlights: ► Kinetic and mechanism of the gas-phase thermolysis of tetroxane were determined. ► Gas chromatography and computational potential energy surfaces were performed. ► A mechanism in steps looked like the most probable mechanism. ► A spin–orbit coupling appeared at the singlet and triple diradical open structures. ► A non-adiabatic crossing from the singlet to the triplet state occurred. - Abstract: Gas-phase thermolysis reaction of formaldehyde diperoxide (1,2,4,5-tetroxane) was performed in an injection chamber of a gas chromatograph at a range of 463–503 K. The average Arrhenius activation energy and pre-exponential factor were 29.3 ± 0.8 kcal/mol and 5.2 × 10 13 s −1 , respectively. Critical points and reaction paths of the ground singlet and first triplet potential energy surfaces (PES) were calculated, using DFT method at BHANDHLYP/6-311+G ∗∗ level of the theory. Also, G3 calculations were performed on the reactant and products. Reaction by the ground-singlet and first-triplet states turned out to be endothermic and exothermic, respectively. The mechanism in three steps seemed to be the most probable one. An electronically non-adiabatic process appeared, in which a crossing, at an open diradical structure, from the singlet to the triplet state PES occurred, due to a spin–orbit coupling, yielding an exothermic reaction. Theoretical kinetic constant coming from the non- adiabatic transition from the singlet to the triplet state agrees with the experimental values.

  6. Study on the kinetics of gel formation in the radiation crosslinking reaction

    International Nuclear Information System (INIS)

    Wang Mingjun; Liu Yuming

    1988-01-01

    From the kinetic equation of gel formation obtained by the authors, the mechanism of gel formation may be interpreted clearly as follows: (1) When the degree of crosslinking q g , the system is sol and the crosslinking reaction is only carried out between the sol molecules. (q g is the gel point). (2) When q=q g , there exists a beginning point where the gel is coexisted with the sol, and the system is still sol, and the crosslinking reaction is still carried out between the sol molecules. (3) When q>q g , the crosslinking reaction exceeds the gel point and the gel is coexisted with the sol. The kinetic equation shows clearly that the transformation from sol into gel is caused by crosslinking reaction of the uncrosslinked chain units between the sol and gel molecules. As a result the sol molecules are transformed into the gel molecules gradually, and the sol fraction is reduced. When the chain units P-barw(s)S(1-s)dq in sol are crosslinked with gel, the sol fraction in the system is reduced ds (where P-barw(s) is a function of the radiation dose and s is sol frection). The degree of crosslinking per unit dose (q 0 ) is a reduced function of dose (R). The equation for calculating its value for every irradiation dose is obtained. After knowing the correlation between P-bar W(s) vs R and q 0 vs R, the distribution of gel and sol in the process of radiation crosslinking can be discussed as well

  7. Kinetics of the reactions of hydrated electrons with metal complexes

    International Nuclear Information System (INIS)

    Korsse, J.

    1983-01-01

    The reactivity of the hydrated electron towards metal complexes is considered. Experiments are described involving metal EDTA and similar complexes. The metal ions studied are mainly Ni 2+ , Co 2+ and Cu 2+ . Rates of the reactions of the complexes with e - (aq) were measured using the pulse radiolysis technique. It is shown that the reactions of e - (aq) with the copper complexes display unusually small kinetic salt effects. The results suggest long-range electron transfer by tunneling. A tunneling model is presented and the experimental results are discussed in terms of this model. Results of approximate molecular orbital calculations of some redox potentials are given, for EDTA chelates as well as for series of hexacyano and hexaquo complexes. Finally, equilibrium constants for the formation of ternary complexes are reported. (Auth./G.J.P.)

  8. REACTION KINETICS SELF-PROPOGATION REGIME DURING PRE-IGNITION PERIOD

    Directory of Open Access Journals (Sweden)

    D. D. Polishchuk

    2015-11-01

    Full Text Available Self-propagation high temperature synthesis (SHS technological regulations application is mainly limited by transformation processes taking place in the pre-ignition period. Zn-S, Zn-Se, Ti-C and 3Ni-Al small sample systems ignition experimental study was carried out under heating conditions in inert atmosphere with temperature values T = 1200K.It was shown that at this temperature level a chemical reaction can be initiated, turning into a self-sustaining mode. Wherein the reaction limiting factors can be mass transfer processes. Ignition temperatures were determined and plotted via the samples size. A physical ignition model was developed assuming the pre-ignition period limiting reaction Arrhenius law.The inverse combustion problem solution made it possible to calculate the low-temperature (T = 800 ÷ 1200K reaction kinetic constant values. Comparison thus obtained values  with the known data of other researchers showed their good agreement.Activation energy values for the Zn-S system were used to calculate the heat wave propagation speed. This value appeared to coincide with experimental values.Obtained results analysis leads to the conclusion about the availability and justification for the proposed method of express-analysis of presupposed, but previously not studied SHS systems. The results thus obtained allow us to estimate conditions for the SHS technology implementation, the reactor characteristic sizes and the thermal wave’s propagation speed.

  9. Cluster dynamics models of irradiation damage accumulation in ferritic iron. II. Effects of reaction dimensionality

    Energy Technology Data Exchange (ETDEWEB)

    Kohnert, Aaron A.; Wirth, Brian D. [University of Tennessee, Knoxville, Tennessee 37996-2300 (United States)

    2015-04-21

    The black dot damage features which develop in iron at low temperatures exhibit significant mobility during in situ irradiation experiments via a series of discrete, intermittent, long range hops. By incorporating this mobility into cluster dynamics models, the temperature dependence of such damage structures can be explained with a surprising degree of accuracy. Such motion, however, is one dimensional in nature. This aspect of the physics has not been fully considered in prior models. This article describes one dimensional reaction kinetics in the context of cluster dynamics and applies them to the black dot problem. This allows both a more detailed description of the mechanisms by which defects execute irradiation-induced hops while allowing a full examination of the importance of kinetic assumptions in accurately assessing the development of this irradiation microstructure. Results are presented to demonstrate whether one dimensional diffusion alters the dependence of the defect population on factors such as temperature and defect hop length. Finally, the size of interstitial loops that develop is shown to depend on the extent of the reaction volumes between interstitial clusters, as well as the dimensionality of these interactions.

  10. Searching out the hydrogen absorption/desorption limiting reaction factors: Strategies allowing to increase kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Zeaiter, Ali, E-mail: ali.zeaiter@femto-st.fr; Chapelle, David; Nardin, Philippe

    2015-10-05

    Highlights: • A macro scale thermodynamic model that simulates the response of a FeTi-X hydride tank is performed, and validated experimentally. • A sensibility study to identify the most influent input variables that can changes very largely the reaction rate. - Abstract: Hydrogen gas has become one of the most promising energy carriers. Main breakthrough concerns hydrogen solid storage, specially based on intermetallic material use. Regarding the raw material abundance and cost, the AB type alloy FeTi is an auspicious candidate to store hydrogen. Its absorption/desorption kinetics is a basic hindrance to common use, compared with more usual hydrides. First, discussions based on literature help us identifying the successive steps leading to metal hydriding, and allow to introduce the physical parameters which drive or limit the reaction. This analysis leads us to suggest strategies in order to increase absorption/desorption kinetics. Attention is then paid to a thermofluidodynamic model, allowing to describe a macroscopic solid storage reactor. Thus, we can achieve a simulation which describes the overall reaction inside the hydrogen reactor and, by varying the sub-mentioned parameters (thermal conductivity, the powder granularity, environment heat exchange…), we attempt to hierarchy the reaction limiting factors. These simulations are correlated to absorption/desorption experiments for which pressure, temperature and hydrogen flow are recorded.

  11. Spectroscopic and Kinetic Characterization of Peroxidase-Like π-Cation Radical Pinch-Porphyrin-Iron(III Reaction Intermediate Models of Peroxidase Enzymes

    Directory of Open Access Journals (Sweden)

    Samuel Hernández Anzaldo

    2016-06-01

    Full Text Available The spectroscopic and kinetic characterization of two intermediates from the H2O2 oxidation of three dimethyl ester [(proto, (meso, (deuteroporphyrinato (picdien]Fe(III complexes ([FePPPic], [FeMPPic] and [FeDPPic], respectively pinch-porphyrin peroxidase enzyme models, with s = 5/2 and 3/2 Fe(III quantum mixed spin (qms ground states is described herein. The kinetic study by UV/Vis at λmax = 465 nm showed two different types of kinetics during the oxidation process in the guaiacol test for peroxidases (1–3 + guaiacol + H2O2 → oxidation guaiacol products. The first intermediate was observed during the first 24 s of the reaction. When the reaction conditions were changed to higher concentration of pinch-porphyrins and hydrogen peroxide only one type of kinetics was observed. Next, the reaction was performed only between pinch-porphyrins-Fe(III and H2O2, resulting in only two types of kinetics that were developed during the first 0–4 s. After this time a self-oxidation process was observed. Our hypotheses state that the formation of the π-cation radicals, reaction intermediates of the pinch-porphyrin-Fe(III family with the ligand picdien [N,N’-bis-pyridin-2-ylmethyl-propane-1,3-diamine], occurred with unique kinetics that are different from the overall process and was involved in the oxidation pathway. UV-Vis, 1H-NMR and ESR spectra confirmed the formation of such intermediates. The results in this paper highlight the link between different spectroscopic techniques that positively depict the kinetic traits of artificial compounds with enzyme-like activity.

  12. Struvite Precipitation and Phosphorous Removal from Urine Synthetic Solution: Reaction Kinetic Study

    Directory of Open Access Journals (Sweden)

    Marwa Saied Shalaby

    2015-03-01

    Full Text Available Phosphorus, like oil, is a non-renewable resource that must be harvested from finite resources in the earth’s crust. An essential element for life, phosphorus is becoming increasingly scarce, contaminated, and difficult to extract. Struvite or magnesium ammonium phosphate (MgNH4PO4.6H2O is a white, crystalline phosphate mineral that can be used as a bio-available fertilizer. The main objective of this research is to indicate the most important operating parameters affecting struvite precipitation by means of chemical reaction kinetics. The present study explores struvite precipitation by chemical method under different starting molar ratios, pH and SSR. It is shown that an increase of starting Mg: PO4: NH4 with respect to magnesium (1.6:1:1 strongly influences the growth rate of struvite and so the efficiency of the phosphate removal. This was attributed to the effect of magnesium on the struvite solubility product and on the reached supersaturation Super Saturation Ratio at optimum starting molar ratio and pH. It was also shown, by using chemical precipitation method that the determined Super Saturation Ratio (SSR values of struvite, at 8, 8.5, 9, 9.5 and 10 are 1.314, 4.29, 8.89, 9.87 and 14.89 respectively are close to those presented in the literature for different origins of wastewater streams. The results show that SSR , pH, and starting molar ratio strongly influences the kinetics of precipitation and so phosphorous removal to reach 93% removal percent , 5.95 mg/lit as a minimum PO4 remained in solution, and 7.9 gm precipitated struvite from feed synthetic solution of 750 ml . The product was subjected to chemical analysis by means of EDIX-FTIR, SEM and XRD showing conformity with published literature. First-order kinetics was found to be sufficient to describe the rate data. The rates increased with increasing pH and so SSR and the apparent rate constants for the reaction were determined. © 2015 BCREC UNDIP. All rights reserved

  13. Prediction of point-defect migration energy barriers in alloys using artificial intelligence for atomistic kinetic Monte Carlo applications

    Energy Technology Data Exchange (ETDEWEB)

    Castin, N. [Structural Materials Group, Nuclear Materials Science Institute, Studiecentrum voor Kerneenergie Centre d' etude de l' energie nucleaire (SCK CEN), Boeretang 200, B-2400 Mol (Belgium); Universite Libre de Bruxelles (ULB), Physique des Solides Irradies et Nanostructures (PSIN), CP234 Boulevard du triomphe, Brussels (Belgium); Malerba, L. [Structural Materials Group, Nuclear Materials Science Institute, Studiecentrum voor Kerneenergie Centre d' etude de l' energie nucleaire (SCK CEN), Boeretang 200, B-2400 Mol (Belgium)], E-mail: lmalerba@sckcen.be

    2009-09-15

    We significantly improved a previously proposed method to take into account chemical and also relaxation effects on point-defect migration energy barriers, as predicted by an interatomic potential, in a rigid lattice atomistic kinetic Monte Carlo simulation. Examples of energy barriers are rigorously calculated, including chemical and relaxation effects, as functions of the local atomic configuration, using a nudged elastic bands technique. These examples are then used to train an artificial neural network that provides the barriers on-demand during the simulation for each configuration encountered by the migrating defect. Thanks to a newly developed training method, the configuration can include a large number of neighbour shells, thereby properly including also strain effects. Satisfactory results have been obtained when the configuration includes different chemical species only. The problems encountered in the extension of the method to configurations including any number of point-defects are stated and solutions to tackle them are sketched.

  14. Displacement cascades and defect annealing in tungsten, Part III: The sensitivity of cascade annealing in tungsten to the values of kinetic parameters

    Energy Technology Data Exchange (ETDEWEB)

    Nandipati, Giridhar, E-mail: giridhar.nandipati@pnnl.gov [Pacific Northwest National Laboratory, Richland, WA (United States); Setyawan, Wahyu; Heinisch, Howard L. [Pacific Northwest National Laboratory, Richland, WA (United States); Roche, Kenneth J. [Pacific Northwest National Laboratory, Richland, WA (United States); Department of Physics, University of Washington, Seattle, WA 98195 (United States); Kurtz, Richard J. [Pacific Northwest National Laboratory, Richland, WA (United States); Wirth, Brian D. [University of Tennessee, Knoxville, TN (United States)

    2015-07-15

    A study has been performed using object kinetic Monte Carlo (OKMC) simulations to investigate various aspects of cascade aging in bulk tungsten (W) and to determine its sensitivity to the kinetic parameters. The primary focus is on how the kinetic parameters affect the intracascade recombination of defects. Results indicate that, due to the disparate mobilities of SIA and vacancy clusters, annealing is dominated by SIA migration even at 2050 K. It was found that for 100 keV cascades initiated at 300 K, recombination is dominated by the annihilation of large defect clusters, while for all the other primary knock-on atom (PKA) energies and temperatures, recombination is primarily due to the migration and rotation of small SIA clusters, while the large SIA clusters escape the simulation cell. The annealing efficiency exhibits an inverse U-shaped curve behavior with increasing temperature, especially at large PKA energies, caused by the asymmetry in SIA and vacancy clustering assisted by the large differences in their mobilities. This behavior is unaffected by the dimensionality of SIA migration, and it persists over a broad range of relative mobilities of SIAs and vacancies.

  15. Kinetic theory of radiation effects

    International Nuclear Information System (INIS)

    Mansur, L.K.

    1987-01-01

    To help achieve the quantitative and mechanistic understanding of these processes, the kinetic theory of radiation effects has been developed in the DOE basic energy sciences radiation effects and fusion reactor materials programs, as well as in corresponding efforts in other countries. This discipline grapples with a very wide range of phenomena and draws on numerous sub-fields of theory such as defect physics, diffusion, elasticity, chemical reaction rates, phase transformations and thermodynamics. The theory is cast in a mathematical framework of continuum dynamics. Issues particularly relevant to the present inquiry can be viewed from the standpoints of applications of the theory and areas requiring further progress

  16. Hydrolysis reaction of 2,4-dichlorophenoxyacetic acid. A kinetic and computational study

    Science.gov (United States)

    Romero, Jorge Marcelo; Jorge, Nelly Lidia; Grand, André; Hernández-Laguna, Alfonso

    2015-10-01

    The degradation of the 2,4-dichlorophenoxyacetic acid in aqueous solution is an hydrolysis reaction. Two products are identified: 2,4-dichlorophenol and glycolic acid. Reaction is investigated as a function of pH and temperature, and it is first-order kinetics and pH-dependent. Reaction is modeled in gas phase, where a proton catalyses the reaction. Critical points of PES are calculated at B3LYP/6-311++G(3df,2p), and aug-cc-pvqz//6-311++G(3df,2p) levels plus ZPE at 6-311++G(3df,2p) level. The activation barrier is 21.2 kcal/mol. Theoretical results agree with the experimental results. A second mechanism related with a Cl2Phsbnd Osbnd CH2sbnd COOH⋯H2O complex is found, but with a rate limiting step of 38.4 kcal/mol.

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

    International Nuclear Information System (INIS)

    Trokhimets, A.I.

    1979-01-01

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

  18. 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

  19. A kinetic study of the redox reactions of complex cyanides of iron, molybdenum and tungsten with compounds of the group VI A elements

    International Nuclear Information System (INIS)

    Dennis, C.R.

    1981-01-01

    The kinetic study arises out of the fact that few is known about redox kinetics of complex cyanides of molybdenum and tungsten. The redox kinetics of the complex cyanides of iron with organic and inorganic compounds are well known in organic chemistry. This comparitive study is done to obtain more information on redox reactions of complex cyanides of molybdenum and tungsten considering its greater applicability in organic and inorganic chemistry because of the propitious reduction potential of this complex cyanide in acidic and alkaline mediums. Various redox systems are kinetically investigated regarding the influence of the oxidising agent, reducing agent hydrogen ions and alkaline-metal ions on the reaction rate. A reaction mechanism is proposed for every system

  20. The role of high temperature heterogeneous reaction kinetics in the rate of radionuclide vaporisation during core-concrete interactions

    International Nuclear Information System (INIS)

    Raymond, D.P.; Clough, P.N.

    1989-09-01

    Heterogeneous reactions may cause enhanced release of radionuclides during the core-concrete interaction (CCl) stage of a PWR severe accident. The VANESA computer code models these CCI releases using chemical equilibrium assumptions; however, the possibility that chemical kinetics could prevent equilibrium from being achieved is considered in this report. Direct experimental evidence is lacking on these reactions. Therefore, some analogues studies are reviewed, including examples of Eyring's surface reaction rate theory; sequential vaporisation-oxidation processes; iron and steelmaking chemistry; radionuclide evaporation from solid UO 2 . This circumstantial evidence appeared to agree with the current assumptions, in VANESA and some UK modelling studies, that mass transfer, rather than chemical kinetics will limit the rate at which equilibrium is attained. (author)

  1. Toward a Kinetic Model for Acrylamide Formation in a Glucose-Asparagine Reaction System

    NARCIS (Netherlands)

    Knol, J.J.; Loon, W.A.M.; Linssen, J.P.H.; Ruck, A.L.; Boekel, van M.A.J.S.

    2005-01-01

    A kinetic model for the formation of acrylamide in a glucose-asparagine reaction system is pro-posed. Equimolar solutions (0.2 M) of glucose and asparagine were heated at different tempera-tures (120-200 C) at pH 6.8. Besides the reactants, acrylamide, fructose, and melanoidins were quantified after

  2. Preclusion of switch behavior in reaction networks with mass-action kinetics

    DEFF Research Database (Denmark)

    Feliu, Elisenda; Wiuf, C.

    2012-01-01

    We study networks taken with mass-action kinetics and provide a Jacobian criterion that applies to an arbitrary network to preclude the existence of multiple positive steady states within any stoichiometric class for any choice of rate constants. We are concerned with the characterization...... precludes the existence of degenerate steady states. Further, we relate injectivity of a network to that of the network obtained by adding outflow, or degradation, reactions for all species....

  3. The browning kinetics of the non-enzymatic browning reaction in L-ascorbic acid/basic amino acid systems

    Directory of Open Access Journals (Sweden)

    Ai-Nong YU

    Full Text Available Abstract Under the conditions of weak basis and the reaction temperature range of 110-150 °C, lysine, arginine and histidine were reacted with L-ascorbic acid at equal amount for 30-150 min, respectively and the formation of browning products was monitored with UV–vis spectrometry. The kinetic characteristics of their non-enzymatic browning reaction were investigated. The study results indicated that the non-enzymatic browning reaction of these three amino acids with L-ascorbic acid to form browning products was zero-order reaction. The apparent activation energies for the formation of browning products from L-ascorbic acid/lysine, L-ascorbic acid/arginine and L-ascorbic acid/histidine systems were 54.94, 50.08 and 35.31kJ/mol. The activation energy data indicated the degree of effects of reaction temperature on non-enzymatic browning reaction. Within the temperature range of 110-150 °C, the reaction rate of L-ascorbic acid/lysine system was the fastest one, followed by that of the L-ascorbic acid/arginine system. The reaction rate of L-ascorbic acid/histidine system was the slowest one. Based on the observed kinetic data, the formation mechanisms of browning products were proposed.

  4. Esterification with ethanol to produce biodiesel from high acidity raw materials. Kinetic studies and analysis of secondary reactions

    Energy Technology Data Exchange (ETDEWEB)

    Pisarello, M.L.; Dalla Costa, B.; Mendow, G.; Querini, C.A. [Instituto de Investigaciones en Catalisis y Petroquimica (INCAPE)-(FIQ-UNL, CONICET), Santiago del Estero 2654-Santa Fe, S3000AOJ (Argentina)

    2010-09-15

    In this work, the esterification reaction of free fatty acids (FFA) in sunflower oil, coconut oil and concentrated FFA, with ethanol, methanol and ethanol 96%, using homogeneous acid catalysts to produce biodiesel is studied. Kinetic parameters are estimated with a simplified model, and then used to predict the reaction behavior. Reactions other than the reversible esterification are considered to explain the behavior that this system displays. Such reactions are the triglycerides conversion by acid catalyzed transesterification and hydrolysis. In addition, we include kinetic studies of the reaction that occur between the sulphuric acid and methanol (or ethanol), forming mono and dialkylsulphates. This reaction produces water and consumes methanol (or ethanol), and consequently has a direct impact in the esterification reaction rate and equilibrium conversion. The concentration of sulphuric acid decreases to less than 50% of the initial value due to the reaction with the alcohol. A minimum in the acidity due to the free fatty acids as a function of time was clearly observed during the reaction, which has not been reported earlier. This behavior is related to the consecutive reactions that take place during the esterification of FFA in the presence of triglycerides. The phase separation due to the presence of water, which is generated during the reaction, is also studied. (author)

  5. Reaction kinetics and modeling of photoinitiated cationic polymerization of an alicyclic based diglycidyl ether

    International Nuclear Information System (INIS)

    Harikrishna, R.; Ponrathnam, S.; Tambe, S.S.

    2014-01-01

    Highlights: • Photocationic polymerization of alicyclic based diglycidyl ether was carried out. • Kinetic parameters were influenced by gelation and diffusional restrictions. • Applicability of autocatalytic model was established by nonlinear regression. • System showed higher activation energy than cycloaliphatic and aromatic diepoxides. -- Abstract: Photoinitiated cationic polymerization of cycloaliphatic diepoxides had received tremendous attention, while studies with lesser polymerizable diglycidyl ethers are comparatively less reported. The present work deals with the photoinitiated cationic polymerization of cyclohexane dimethanol diglycidyl ether followed by estimation of kinetic parameters. The effects of concentration of photoinitiator and temperature on curing performance were studied using photo differential scanning calorimeter or photo DSC with polychromatic radiation. It was observed that the rate of polymerization as well as ultimate conversion increased with increasing concentration of photoinitiator and temperature. The influences of gelation as well as diffusional restrictions have remarkable effect on cure performance. The kinetic parameters as per autocatalytic kinetic model were studied by Levenberg–Marquardt nonlinear regression method instead of conventional linear method for obtaining more accurate values of apparent rate constant. It was observed that the model fits with data from initial stages to almost towards the end of the reaction. The activation energy was found to be higher than the values reported for more reactive cycloaliphatic diepoxides. The value of pre-exponential factor increased with increase in activation energy showing influence of gelation at early stages of reaction

  6. Golden rule kinetics of transfer reactions in condensed phase: The microscopic model of electron transfer reactions in disordered solid matrices

    International Nuclear Information System (INIS)

    Basilevsky, M. V.; Mitina, E. A.; Odinokov, A. V.; Titov, S. V.

    2013-01-01

    The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ 0 =ℏω 0 /k B T where ω 0 is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ 0 0 ≫ 1) temperature ranges. For the first (quasi-classical) kinetic regime, the Redfield approximation to the solution of the relaxation equation proved to be sufficient and efficient in practical applications. The study of the essentially quantum-mechanical low-temperature kinetic regime in its asymptotic limit requires the implementation of the exact relaxation equation. The coherent mechanism providing a non-vanishing reaction rate has been revealed when T→ 0. An accurate computational methodology for the cross-over kinetic regime needs a further elaboration. The original model of the hopping mechanism for electronic conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the kinetic regimes, which are usually postulated in the

  7. The chemical kinetics of the reactions of lithium with steam-air mixtures

    International Nuclear Information System (INIS)

    Barnett, D.S.; Kazimi, M.S.

    1989-04-01

    This work involved the experimental and analytical determination of the consequences of lithium fires in the presence of steam. Experiments were performed to characterize the chemical reactions of lithium with steam-nitrogen and steam-air mixtures. Models were introduced in the LITFIRE code to describe lithium fires in the presence of steam inside the containment building and plasma chamber of a hypothetical fusion reactor. The code was also equipped with the capability to determine the effects of decay heat and lithium fire on the temperature response of the reactor first wall in the event of a coolant disturbance. Forty-two kinetics experiments were performed in which a stream of steam-nitrogen or steam-air was passed over and reacted with approximately three grams of lithium heated to a predetermined temperature. The lithium reaction rates with the constituent gases were measured and characterized for a wide range of lithium temperatures and gas compositions. Experiments were performed with steam molar concentrations of 5, 15 and 30% and lithium temperatures ranging from 400 to 1100 degree C, inclusive. The LITFIRE code was modified to enable it to model the interactions of lithium with steam-air atmospheres. Results of the reaction kinetics experiments were used in the reaction model, and the heat transfer model was expanded to allow it to handle condensible atmospheres. Three groups of accidents were investigated: a spill on the containment building floor, a spill inside the reactor plasma chamber, and a spill inside the plasma chamber with steam injection to the containment building simulating a steam line break. The results were compared to dry air cases under the same conditions. 23 refs., 66 figs., 18 tabs

  8. Gas-phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Jorge, Nelly Lidia [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain); Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Romero, Jorge Marcelo [Area de Quimica Fisica Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Avda. Libertad 5460, 3400 Corrientes (Argentina); Grand, Andre [INAC, SCIB, Laboratoire ' Lesions des Acides Nucleiques' , UMR CEA-UJF E3, CEA-Grenoble, 17 Rue des Martyrs, 38054 Grenoble cedex 9 (France); Hernandez-Laguna, Alfonso, E-mail: ahlaguna@ugr.es [Instituto Andaluz de Ciencias de la Tierra, CSIC-Universidad de Granada, Av. Las Palmeras 4, 18100 Armilla, Granada (Spain)

    2012-01-17

    Highlights: Black-Right-Pointing-Pointer Kinetic and mechanism of the gas-phase thermolysis of tetroxane were determined. Black-Right-Pointing-Pointer Gas chromatography and computational potential energy surfaces were performed. Black-Right-Pointing-Pointer A mechanism in steps looked like the most probable mechanism. Black-Right-Pointing-Pointer A spin-orbit coupling appeared at the singlet and triple diradical open structures. Black-Right-Pointing-Pointer A non-adiabatic crossing from the singlet to the triplet state occurred. - Abstract: Gas-phase thermolysis reaction of formaldehyde diperoxide (1,2,4,5-tetroxane) was performed in an injection chamber of a gas chromatograph at a range of 463-503 K. The average Arrhenius activation energy and pre-exponential factor were 29.3 {+-} 0.8 kcal/mol and 5.2 Multiplication-Sign 10{sup 13} s{sup -1}, respectively. Critical points and reaction paths of the ground singlet and first triplet potential energy surfaces (PES) were calculated, using DFT method at BHANDHLYP/6-311+G{sup Asterisk-Operator Asterisk-Operator} level of the theory. Also, G3 calculations were performed on the reactant and products. Reaction by the ground-singlet and first-triplet states turned out to be endothermic and exothermic, respectively. The mechanism in three steps seemed to be the most probable one. An electronically non-adiabatic process appeared, in which a crossing, at an open diradical structure, from the singlet to the triplet state PES occurred, due to a spin-orbit coupling, yielding an exothermic reaction. Theoretical kinetic constant coming from the non- adiabatic transition from the singlet to the triplet state agrees with the experimental values.

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

    International Nuclear Information System (INIS)

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

    1978-01-01

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

  10. Programming chemical kinetics: engineering dynamic reaction networks with DNA strand displacement

    Science.gov (United States)

    Srinivas, Niranjan

    Over the last century, the silicon revolution has enabled us to build faster, smaller and more sophisticated computers. Today, these computers control phones, cars, satellites, assembly lines, and other electromechanical devices. Just as electrical wiring controls electromechanical devices, living organisms employ "chemical wiring" to make decisions about their environment and control physical processes. Currently, the big difference between these two substrates is that while we have the abstractions, design principles, verification and fabrication techniques in place for programming with silicon, we have no comparable understanding or expertise for programming chemistry. In this thesis we take a small step towards the goal of learning how to systematically engineer prescribed non-equilibrium dynamical behaviors in chemical systems. We use the formalism of chemical reaction networks (CRNs), combined with mass-action kinetics, as our programming language for specifying dynamical behaviors. Leveraging the tools of nucleic acid nanotechnology (introduced in Chapter 1), we employ synthetic DNA molecules as our molecular architecture and toehold-mediated DNA strand displacement as our reaction primitive. Abstraction, modular design and systematic fabrication can work only with well-understood and quantitatively characterized tools. Therefore, we embark on a detailed study of the "device physics" of DNA strand displacement (Chapter 2). We present a unified view of strand displacement biophysics and kinetics by studying the process at multiple levels of detail, using an intuitive model of a random walk on a 1-dimensional energy landscape, a secondary structure kinetics model with single base-pair steps, and a coarse-grained molecular model that incorporates three-dimensional geometric and steric effects. Further, we experimentally investigate the thermodynamics of three-way branch migration. Our findings are consistent with previously measured or inferred rates for

  11. Kinetics of heterogeneous chemical reactions: a theoretical model for the accumulation of pesticides in soil.

    Science.gov (United States)

    Lin, S H; Sahai, R; Eyring, H

    1971-04-01

    A theoretical model for the accumulation of pesticides in soil has been proposed and discussed from the viewpoint of heterogeneous reaction kinetics with a basic aim to understand the complex nature of soil processes relating to the environmental pollution. In the bulk of soil, the pesticide disappears by diffusion and a chemical reaction; the rate processes considered on the surface of soil are diffusion, chemical reaction, vaporization, and regular pesticide application. The differential equations involved have been solved analytically by the Laplace-transform method.

  12. Tunneling and reflection in unimolecular reaction kinetic energy release distributions

    Science.gov (United States)

    Hansen, K.

    2018-02-01

    The kinetic energy release distributions in unimolecular reactions is calculated with detailed balance theory, taking into account the tunneling and the reflection coefficient in three different types of transition states; (i) a saddle point corresponding to a standard RRKM-type theory, (ii) an attachment Langevin cross section, and (iii) an absorbing sphere potential at short range, without long range interactions. Corrections are significant in the one dimensional saddle point states. Very light and lightly bound absorbing systems will show measurable effects in decays from the absorbing sphere, whereas the Langevin cross section is essentially unchanged.

  13. Kinetics of the glucose/glycine Maillard reaction pathways: influences of pH and reactant initial concentrations

    NARCIS (Netherlands)

    Martins, S.I.F.S.; Boekel, van M.A.J.S.

    2005-01-01

    A previously proposed kinetic model for the glucose/glycine Maillard reaction pathways has been validated by changing the initial pH (4.8, 5.5, 6.0, 6.8 and 7.5) of the reaction and reactant initial concentrations (1:2 and 2:1 molar ratios were compared to the 1:1 ratio). The model consists of 10

  14. Synthesis Of Magnesium-Aluminum Layered Double Hydroxides By Mechanochemical Method And Its Solid State Reaction Kinetics

    Directory of Open Access Journals (Sweden)

    Hongbo Y.

    2015-06-01

    Full Text Available A mechanochemical method is developed in preparing magnesium-aluminum-layered double hydroxides (MgAl-LDHs. This approach includes activation process and diffusion process. In order to verify the LDHs structure and study the reaction kinetics, X-ray diffraction (XRD patterns, inductively coupled plasma(ICP and physical adsorption instrument were characterized. The results show that activation time can change the surface of particles and affect the reaction grade. During the diffusion process, reaction time is the most important factor. The reaction energy (ΔQ was calculated that is 6kJ/mol.

  15. 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

  16. Twin defects engineered Pd cocatalyst on C3N4 nanosheets for enhanced photocatalytic performance in CO2 reduction reaction

    Science.gov (United States)

    Lang, Qingqing; Hu, Wenli; Zhou, Penghui; Huang, Tianlong; Zhong, Shuxian; Yang, Lining; Chen, Jianrong; Bai, Song

    2017-12-01

    Photocatalytic conversion of CO2 to value-added chemicals, a potential route to addressing the depletion of fossil fuels and anthropogenic climate change, is greatly limited by the low-efficient semiconductor photocatalyst. The integration of cocatalyst with light-harvesting semiconductor is a promising approach to enhancing the photocatalytic performance in CO2 reduction reaction. The enhancement is greatly determined by the catalytic active sites on the surface of cocatalyst. Herein, we demonstrate that the photocatalytic performance in the CO2 reduction reaction is greatly promoted by twin defects engineered Pd cocatalyst. In this work, Pd nanoicosahedrons with twin defects were in situ grown on C3N4 nanosheets, which effectively improve the photocatalytic performance in reduction of CO2 to CO and CH4 in comparison with Pd nanotetrahedrons without twin defects. It is proposed that the twin boundary (TB) terminations on the surface of Pd cocatalysts are highly catalytic active sites for CO2 reduction reaction. Based on the proposed mechanism, the photocatalytic activity and selectivity in CO2 reduction were further advanced through reducing the size of Pd icosahedral cocatalyst resulted from the increased surface density of TB terminations. The defect engineering on the surface of cocatalyst represents a novel route in realizing high-performance photocatalytic applications.

  17. Kinetic modeling of electron transfer reactions in photosystem I complexes of various structures with substituted quinone acceptors.

    Science.gov (United States)

    Milanovsky, Georgy E; Petrova, Anastasia A; Cherepanov, Dmitry A; Semenov, Alexey Yu

    2017-09-01

    The reduction kinetics of the photo-oxidized primary electron donor P 700 in photosystem I (PS I) complexes from cyanobacteria Synechocystis sp. PCC 6803 were analyzed within the kinetic model, which considers electron transfer (ET) reactions between P 700 , secondary quinone acceptor A 1 , iron-sulfur clusters and external electron donor and acceptors - methylviologen (MV), 2,3-dichloro-naphthoquinone (Cl 2 NQ) and oxygen. PS I complexes containing various quinones in the A 1 -binding site (phylloquinone PhQ, plastoquinone-9 PQ and Cl 2 NQ) as well as F X -core complexes, depleted of terminal iron-sulfur F A /F B clusters, were studied. The acceleration of charge recombination in F X -core complexes by PhQ/PQ substitution indicates that backward ET from the iron-sulfur clusters involves quinone in the A 1 -binding site. The kinetic parameters of ET reactions were obtained by global fitting of the P 700 + reduction with the kinetic model. The free energy gap ΔG 0 between F X and F A /F B clusters was estimated as -130 meV. The driving force of ET from A 1 to F X was determined as -50 and -220 meV for PhQ in the A and B cofactor branches, respectively. For PQ in A 1A -site, this reaction was found to be endergonic (ΔG 0  = +75 meV). The interaction of PS I with external acceptors was quantitatively described in terms of Michaelis-Menten kinetics. The second-order rate constants of ET from F A /F B , F X and Cl 2 NQ in the A 1 -site of PS I to external acceptors were estimated. The side production of superoxide radical in the A 1 -site by oxygen reduction via the Mehler reaction might comprise ≥0.3% of the total electron flow in PS I.

  18. Thermodynamic and kinetic properties of intrinsic defects and Mg transmutants in 3C–SiC determined by density functional theory

    International Nuclear Information System (INIS)

    Hu, Shenyang; Setyawan, Wahyu; Van Ginhoven, Renee M.; Jiang, Weilin; Henager, Charles H.; Kurtz, Richard J.

    2014-01-01

    Density functional theory (DFT) is used to calculate the thermodynamic and kinetic properties of transmutant Mg in 3C–SiC due to high-energy neutron irradiation associated with the fusion nuclear environment. The formation and binding energies of intrinsic defects, Mg-related defects, and clusters in 3C–SiC are systematically calculated. The minimum energy paths and activation energies during point defect migration and small cluster evolution are studied using a generalized solid-state nudged elastic band (G-SSNEB) method with DFT energy calculations. Stable defect structures and possible defect migration mechanisms are identified. The evolution of binding energies during Mg 2 Si formation demonstrates that the formation of Mg 2 Si needs to overcome a critical nucleus size and nucleation barrier. It is found that C vacancies promote the formation of the Mg 2 Si nucleus, and formation of which results in a compressive stress field around the nucleus. These data are important inputs in meso- and macro-scale modeling and experiments to understand and predict the impact of Mg on phase stability, microstructure evolution, and performance of SiC and SiC-based materials during long-term neutron exposures

  19. Kinetics of the reactions of bromine atoms with a series of aliphatic aldehydes at 298 K

    Energy Technology Data Exchange (ETDEWEB)

    Szilagyi, I.; Imrik, K.; Dobe, S.; Berces, T. [Magyar Tudomanyos Akademia, Budapest (Hungary). Koezponti Kemiai Kutato Intezete

    1998-01-01

    The kinetics of the reactions of Br({sup 2}P{sub 3/2}) with selected aldehydes, i.e. ethanal (1), propanal (2), 2-methyl-propanal (3), 2.2-dimethyl-propanal (4) and trichloroacetaldehyde (5) were studied at 298{+-}2 K. Rate constants for overall reactions were measured using the fast flow technique with resonance fluorescence detection of Br. Complementary determinations were carried out by the laser flash photolysis method. The following rate constants were obtained in the kinetic measurements ({+-}2{sigma}): k{sub 1}=(2.1{+-}0.2) x 10{sup 12}, k{sub 2}=(4.3{+-}0.4) x 10{sup 12}, k{sub 3}=(6.3{+-}1.4) x 10{sup 12}, k{sub 4}=(8.5{+-}0.8) x 10{sup 12}, k{sub 5}{<=}1 x 10{sup 9}, all in cm{sup 3}mol{sup -1}s{sup -1} units. The probable mechanism for the reactions of bromine atoms with aliphatic aldehydes has been discussed. (orig.)

  20. Flow chemistry kinetic studies reveal reaction conditions for ready access to unsymmetrical trehalose analogues.

    Science.gov (United States)

    Patel, Mitul K; Davis, Benjamin G

    2010-10-07

    Monofunctionalization of trehalose, a widely-found symmetric plant disaccharide, was studied in a microreactor to give valuable kinetic insights that have allowed improvements in desymmetrization yields and the development of a reaction sequence for large scale monofunctionalizations that allow access to probes of trehalose's biological function.

  1. Kinetics of the monomer-dimer reaction of yeast hexokinase PI.

    Science.gov (United States)

    Hoggett, J G; Kellett, G L

    1992-10-15

    Kinetic studies of the glucose-dependent monomer-dimer reaction of yeast hexokinase PI at pH 8.0 in the presence of 0.1 M-KCl have been carried out using the fluorescence temperature-jump technique. A slow-relaxation effect was observed which was attributed from its dependence on enzyme concentration to the monomer-dimer reaction; the reciprocal relaxation times tau-1 varied from 3 s-1 at low concentrations of glucose to 42 s-1 at saturating concentrations. Rate constants for association (kass.) and dissociation (kdiss.) were determined as a function of glucose concentration using values of the equilibrium association constant of the monomer-dimer reaction derived from sedimentation ultracentrifugation studies under similar conditions, and also from the dependence of tau-2 on enzyme concentration. kass. was almost independent of glucose concentration and its value (2 x 10(5) M-1.s-1) was close to that expected for a diffusion-controlled process. The influence of glucose on the monomer-dimer reaction is entirely due to effects on kdiss., which increases from 0.21 s-1 in the absence of glucose to 25 s-1 at saturating concentrations. The monomer and dimer forms of hexokinase have different affinities and Km values for glucose, and the results reported here imply that there may be a significant lag in the response of the monomer-dimer reaction to changes in glucose concentrations in vivo with consequent hysteretic effects on the hexokinase activity.

  2. A kinetic study of the reaction of water vapor and carbon dioxide on uranium

    International Nuclear Information System (INIS)

    Santon, J.P.

    1964-09-01

    The kinetic study of the reaction of water vapour and carbon dioxide with uranium has been performed by thermogravimetric methods at temperatures between 160 and 410 deg G in the first case, 350 and 1050 deg C in the second: Three sorts of uranium specimens were used: uranium powder, thin evaporated films, and small spheres obtained from a plasma furnace. The experimental results led in the case of water vapour, to a linear rate of reaction controlled by diffusion at the lower temperatures, and by a surface reaction at the upper ones. In the case of carbon dioxide, a parabolic law has been found, controlled by diffusional processes. (author) [fr

  3. 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)

  4. Kinetic study of the Diels-Alder reaction of Li⁺@C₆₀ with cyclohexadiene: greatly increased reaction rate by encapsulated Li⁺.

    Science.gov (United States)

    Ueno, Hiroshi; Kawakami, Hiroki; Nakagawa, Koji; Okada, Hiroshi; Ikuma, Naohiko; Aoyagi, Shinobu; Kokubo, Ken; Matsuo, Yutaka; Oshima, Takumi

    2014-08-06

    We studied the kinetics of the Diels-Alder reaction of Li(+)-encapsulated [60]fullerene with 1,3-cyclohexadiene and characterized the obtained product, [Li(+)@C60(C6H8)](PF6(-)). Compared with empty C60, Li(+)@C60 reacted 2400-fold faster at 303 K, a rate enhancement that corresponds to lowering the activation energy by 24.2 kJ mol(-1). The enhanced Diels-Alder reaction rate was well explained by DFT calculation at the M06-2X/6-31G(d) level of theory considering the reactant complex with dispersion corrections. The calculated activation energies for empty C60 and Li(+)@C60 (65.2 and 43.6 kJ mol(-1), respectively) agreed fairly well with the experimentally obtained values (67.4 and 44.0 kJ mol(-1), respectively). According to the calculation, the lowering of the transition state energy by Li(+) encapsulation was associated with stabilization of the reactant complex (by 14.1 kJ mol(-1)) and the [4 + 2] product (by 5.9 kJ mol(-1)) through favorable frontier molecular orbital interactions. The encapsulated Li(+) ion catalyzed the Diels-Alder reaction by lowering the LUMO of Li(+)@C60. This is the first detailed report on the kinetics of a Diels-Alder reaction catalyzed by an encapsulated Lewis acid catalyst rather than one coordinated to a heteroatom in the dienophile.

  5. Displacement cascades and defect annealing in tungsten, Part II: Object kinetic Monte Carlo simulation of tungsten cascade aging

    Energy Technology Data Exchange (ETDEWEB)

    Nandipati, Giridhar, E-mail: giridhar.nandipati@pnnl.gov [Pacific Northwest National Laboratory, Richland, WA (United States); Setyawan, Wahyu; Heinisch, Howard L. [Pacific Northwest National Laboratory, Richland, WA (United States); Roche, Kenneth J. [Pacific Northwest National Laboratory, Richland, WA (United States); Department of Physics, University of Washington, Seattle, WA 98195 (United States); Kurtz, Richard J. [Pacific Northwest National Laboratory, Richland, WA (United States); Wirth, Brian D. [University of Tennessee, Knoxville, TN (United States)

    2015-07-15

    The results of object kinetic Monte Carlo (OKMC) simulations of the annealing of primary cascade damage in bulk tungsten using a comprehensive database of cascades obtained from molecular dynamics (Setyawan et al.) are described as a function of primary knock-on atom (PKA) energy at temperatures of 300, 1025 and 2050 K. An increase in SIA clustering coupled with a decrease in vacancy clustering with increasing temperature, in addition to the disparate mobilities of SIAs versus vacancies, causes an interesting effect of temperature on cascade annealing. The annealing efficiency (the ratio of the number of defects after and before annealing) exhibits an inverse U-shape curve as a function of temperature. The capabilities of the newly developed OKMC code KSOME (kinetic simulations of microstructure evolution) used to carry out these simulations are described.

  6. Displacement cascades and defect annealing in tungsten, Part II: Object kinetic Monte Carlo Simulation of Tungsten Cascade Aging

    Energy Technology Data Exchange (ETDEWEB)

    Nandipati, Giridhar; Setyawan, Wahyu; Heinisch, Howard L.; Roche, Kenneth J.; Kurtz, Richard J.; Wirth, Brian D.

    2015-07-01

    The results of object kinetic Monte Carlo (OKMC) simulations of the annealing of primary cascade damage in bulk tungsten using a comprehensive database of cascades obtained from molecular dynamics (Setyawan et al.) are described as a function of primary knock-on atom (PKA) energy at temperatures of 300, 1025 and 2050 K. An increase in SIA clustering coupled with a decrease in vacancy clustering with increasing temperature, in addition to the disparate mobilities of SIAs versus vacancies, causes an interesting effect of temperature on cascade annealing. The annealing efficiency (the ratio of the number of defects after and before annealing) exhibits an inverse U-shape curve as a function of temperature. The capabilities of the newly developed OKMC code KSOME (kinetic simulations of microstructure evolution) used to carry out these simulations are described.

  7. SUPECA kinetics for scaling redox reactions in networks of mixed substrates and consumers and an example application to aerobic soil respiration

    Science.gov (United States)

    Tang, Jin-Yun; Riley, William J.

    2017-09-01

    Several land biogeochemical models used for studying carbon-climate feedbacks have begun explicitly representing microbial dynamics. However, to our knowledge, there has been no theoretical work on how to achieve a consistent scaling of the complex biogeochemical reactions from microbial individuals to populations, communities, and interactions with plants and mineral soils. We focus here on developing a mathematical formulation of the substrate-consumer relationships for consumer-mediated redox reactions of the form A + BE→ products, where products could be, e.g., microbial biomass or bioproducts. Under the quasi-steady-state approximation, these substrate-consumer relationships can be formulated as the computationally difficult full equilibrium chemistry problem or approximated analytically with the dual Monod (DM) or synthesizing unit (SU) kinetics. We find that DM kinetics is scaling inconsistently for reaction networks because (1) substrate limitations are not considered, (2) contradictory assumptions are made regarding the substrate processing rate when transitioning from single- to multi-substrate redox reactions, and (3) the product generation rate cannot be scaled from one to multiple substrates. In contrast, SU kinetics consistently scales the product generation rate from one to multiple substrates but predicts unrealistic results as consumer abundances reach large values with respect to their substrates. We attribute this deficit to SU's failure to incorporate substrate limitation in its derivation. To address these issues, we propose SUPECA (SU plus the equilibrium chemistry approximation - ECA) kinetics, which consistently imposes substrate and consumer mass balance constraints. We show that SUPECA kinetics satisfies the partition principle, i.e., scaling invariance across a network of an arbitrary number of reactions (e.g., as in Newton's law of motion and Dalton's law of partial pressures). We tested SUPECA kinetics with the equilibrium chemistry

  8. Golden rule kinetics of transfer reactions in condensed phase: The microscopic model of electron transfer reactions in disordered solid matrices

    Energy Technology Data Exchange (ETDEWEB)

    Basilevsky, M. V.; Mitina, E. A. [Photochemistry Center, Russian Academy of Sciences, 7a, Novatorov ul., Moscow (Russian Federation); Odinokov, A. V. [Photochemistry Center, Russian Academy of Sciences, 7a, Novatorov ul., Moscow (Russian Federation); National Research Nuclear University “MEPhI,” 31, Kashirskoye shosse, Moscow (Russian Federation); Titov, S. V. [Karpov Institute of Physical Chemistry, 3-1/12, Building 6, Obuha pereulok, Moscow (Russian Federation)

    2013-12-21

    The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ{sub 0}=ℏω{sub 0}/k{sub B}T where ω{sub 0} is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ{sub 0} < 1 − 3) and for low (ξ{sub 0}≫ 1) temperature ranges. For the first (quasi-classical) kinetic regime, the Redfield approximation to the solution of the relaxation equation proved to be sufficient and efficient in practical applications. The study of the essentially quantum-mechanical low-temperature kinetic regime in its asymptotic limit requires the implementation of the exact relaxation equation. The coherent mechanism providing a non-vanishing reaction rate has been revealed when T→ 0. An accurate computational methodology for the cross-over kinetic regime needs a further elaboration. The original model of the hopping mechanism for electronic conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the

  9. Reaction kinetics of irradiation prepolymerized MMA-PU IPN by 5DXC FTIR

    International Nuclear Information System (INIS)

    Wu Yiming; Zhang Zhiping; Luo Ning

    2000-01-01

    The reaction kinetics of irradiation-prepolymerized MMA-PU (polyether) IPNs have been studied by FTIR. The results indicate that the polymerization of each component in the IPN follows its normal distinct reaction mechanism with no mutual interference. Increasing the concentration of TMPTAM (crosslinking agent of PMMA) increased the formation rate of PMMA, while the formation rate of PU networks remained almost the same. Increasing the concentration of TMP (crosslinking agent of PU) increased the formation rate of PU, while the formation rate of PMMA networks decreased. The formation rate of PU was obviously faster than that of PMMA. A theory for the cage effect of the PU network has been proposed. (author)

  10. The reaction kinetics of lithium salt with water vapor

    International Nuclear Information System (INIS)

    Balooch, M.; Dinh, L.N.; Calef, D.F.

    2002-01-01

    The interaction of lithium salt (LiH and/or LiD) with water vapor in the partial pressure range of 10 -5 -2657 Pa has been investigated. The reaction probability of water with LiH cleaved in an ultra high vacuum environment was obtained using the modulated molecular beam technique. This probability was 0.11 and independent of LiH surface temperature, suggesting a negligible activation energy for the reaction in agreement with quantum chemical calculations. The value gradually reduced, however, to 0.007 as the surface concentration of oxygen containing product approached full coverage. As the film grew beyond a monolayer, the phase lag of hydrogen product increased from 0 deg. C to 20 deg. C and the reaction probability reduced further until it approached our detection limit (∼10 -4 ). This phase lag was attributed to a diffusion-limited process in this regime. For micrometer thick hydroxide films grown in high moisture concentration environment on LiD and LiH, the reaction probability reduced to ∼4x10 -7 and was independent of exposure time. In this regime of thick hydroxide films (LiOH and/or LiOD), microcracks generated in the films to release stress provided easier pathways for moisture to reach the interface. A modified microscope, capable of both atomic force microscopy and nanoindentation, was also employed to investigate the surface morphology of hydroxide monohydrate (LiOH · H 2 O and/or LiOD · H 2 O) grown on hydroxide at high water vapor partial pressures and the kinetics of this growth

  11. Process and kinetics of the fundamental radiation-electrochemical reactions in the primary coolant loop of nuclear reactors

    International Nuclear Information System (INIS)

    Kozomara-Maic, S.

    1987-06-01

    In spite of the rather broad title of this report, its major part is devoted to the corrosion problems at the RA reactor, i.e. causes and consequences of the reactor shutdown in 1979 and 1982. Some problems of reactor chemistry are pointed out because they are significant for future reactor operation. The final conclusion of this report is that corrosion processes in the primary coolant circuit of the nuclear reactor are specific and that radiation effects cannot be excluded when processes and reaction kinetics are investigated. Knowledge about the kinetics of all the chemical reactions occurring in the primary coolant loop are of crucial significance for safe and economical reactor operation [sr

  12. Laccase-catalyzed removal of the antimicrobials chlorophene and dichlorophen from water: Reaction kinetics, pathway and toxicity evaluation.

    Science.gov (United States)

    Shi, Huanhuan; Peng, Jianbiao; Li, Jianhua; Mao, Liang; Wang, Zunyao; Gao, Shixiang

    2016-11-05

    As active agents in cleaning and disinfecting products, antimicrobials have been widely spread in the environment and have drawn extensive attention as potential threats to the ecological system and human health. In this study, the laccase-catalyzed removal of two emerging antimicrobials, chlorophene (CP) and dichlorophen (DCP), was investigated under simulated environmental conditions. Intrinsic reaction kinetics showed that the removal of CP and DCP followed second-order reaction kinetics, first-order with respect to both the enzyme and the substrate concentration. It was also found that fulvic acid could suppress the transformation of CP and DCP by reversing the oxidation reactions through its action as a scavenger of the free radical intermediates produced from reactions between laccase and the substrates. Several reaction products were identified by a quadrupole time-of-flight mass spectrometer, and detailed reaction pathways were proposed. For both CP and DCP, direct polymerization was the principal pathway, and the coupling patterns were further corroborated based on molecular modeling. The nucleophilic substitution of chlorine by the hydroxyl group was observed, and further oxidation products capable of coupling with each other were also found. Additionally, toxicity evaluation tests using Scenedesmus obliquus confirmed that the toxicity of CP and DCP was effectively eliminated during the reaction processes. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Kinetics in radiation chemistry

    International Nuclear Information System (INIS)

    Hummel, A.

    1987-01-01

    In this chapter the authors first briefly review the kinetics of first- and second-order processes for continuous and pulsed irradiation, without taking the effects of nonhomogeneous formation of the species into consideration. They also discuss diffusion controlled reactions under conditions where interactions of more than two particles can be neglected, first the kinetics of the diffusion-controlled reaction of randomly generated species (homogeneous reaction) and then that of isolated pairs of reactants. The latter is often called geminate kinetics when dealing with pairs of oppositely charged species; they shall use this term for the kinetics of isolated pairs in general. In the last section they discuss briefly the kinetics of groups of more than two reactants

  14. Kinetics of the reaction of CH3O2 radicals with NO2

    DEFF Research Database (Denmark)

    Wallington, T.J.; Nielsen, O.J.; Sehested, K.

    1999-01-01

    The kinetics of the gas-phase reaction of CH3O2 radicals with NO2 were studied at 295 K in 0.5-14 arm of SF6 diluent using pulse radiolysis combined with time-resolved UV-VIS spectroscopy. Rate data were obtained by following the loss of CH3O2 using a monitoring wavelength of 260 nm. The results...

  15. Coupling of kinetic Monte Carlo simulations of surface reactions to transport in a fluid for heterogeneous catalytic reactor modeling

    International Nuclear Information System (INIS)

    Schaefer, C.; Jansen, A. P. J.

    2013-01-01

    We have developed a method to couple kinetic Monte Carlo simulations of surface reactions at a molecular scale to transport equations at a macroscopic scale. This method is applicable to steady state reactors. We use a finite difference upwinding scheme and a gap-tooth scheme to efficiently use a limited amount of kinetic Monte Carlo simulations. In general the stochastic kinetic Monte Carlo results do not obey mass conservation so that unphysical accumulation of mass could occur in the reactor. We have developed a method to perform mass balance corrections that is based on a stoichiometry matrix and a least-squares problem that is reduced to a non-singular set of linear equations that is applicable to any surface catalyzed reaction. The implementation of these methods is validated by comparing numerical results of a reactor simulation with a unimolecular reaction to an analytical solution. Furthermore, the method is applied to two reaction mechanisms. The first is the ZGB model for CO oxidation in which inevitable poisoning of the catalyst limits the performance of the reactor. The second is a model for the oxidation of NO on a Pt(111) surface, which becomes active due to lateral interaction at high coverages of oxygen. This reaction model is based on ab initio density functional theory calculations from literature.

  16. Kinetics and mechanisms of iron redox reactions in silicate melts: The effects of temperature and alkali cations

    Energy Technology Data Exchange (ETDEWEB)

    Magnien, V.; Pinet, O. [CEA VALRHO, SCDV/LEBV, F-30207 Bagnols Sur Ceze, (France); Magnien, V.; Neuville, D. R.; Roux, J.; Richet, P. [IPGP, CNRS, Physique des Mineraux et Magmas, F-75252 Paris 05, (France); Cormier, L. [Univ Paris 06, IMPMC, F-75015 Paris, (France); Hazemann, J. L. [CNRS, Inst Neel, F-38043 Grenoble, (France); De Ligny, D. [Univ Lyon 1, LMLC, CNRS, UMR 5620, F-69622 Villeurbanne, (France); Pascarelli, S. [European Synchrotron Radiat Facil, F-38043 Grenoble, (France); Vickridge, I. [Univ Paris 06, INSP, F-75015 Paris, (France)

    2008-07-01

    The kinetics and the mechanisms of iron redox reactions in molten Fe-bearing pyroxene compositions have been investigated by Raman spectroscopy and X-ray absorption Near Edge Structure (XANES) experiments at the iron K-edge. The former experiments have been made only near the glass transition whereas the latter have also been performed from about 1300 to 2100 K. The same kinetics are observed with both techniques. They are described by characteristic times that depend primarily on temperature and not on the initial redox state. At high temperatures, where both kinds of reactions could be investigated, these times are similar for oxidation and reduction. From these characteristic times we have calculated as a function of temperature and composition a parameter termed effective redox diffusivity. For a given melt, the diffusivities follow two distinct Arrhenius laws, which indicate that the mechanisms of the redox reaction are not the same near the glass transition and at high temperatures. As is now well established, diffusion of divalent cations is the dominant mechanism at low temperatures but the enhanced kinetics observed for alkali-bearing melts indicate that Li{sup +} and Na{sup +} also participate in ionic transport. At super-liquidus temperatures, in contrast, diffusion of oxygen represents the dominant mechanism. (authors)

  17. Modeling Ignition of a Heptane Isomer: Improved Thermodynamics, Reaction Pathways, Kinetic, and Rate Rule Optimizations for 2-Methylhexane

    KAUST Repository

    Mohamed, Samah; Cai, Liming; Khaled, Fathi; Banyon, Colin; Wang, Zhandong; Rachidi, Mariam El; Pitsch, Heinz; Curran, Henry J.; Farooq, Aamir; Sarathy, Mani

    2016-01-01

    Accurate chemical kinetic combustion models of lightly branched alkanes (e.g., 2-methylalkanes) are important to investigate the combustion behavior of real fuels. Improving the fidelity of existing kinetic models is a necessity, as new experiments and advanced theories show inaccuracies in certain portions of the models. This study focuses on updating thermodynamic data and the kinetic reaction mechanism for a gasoline surrogate component, 2-methylhexane, based on recently published thermodynamic group values and rate rules derived from quantum calculations and experiments. Alternative pathways for the isomerization of peroxy-alkylhydroperoxide (OOQOOH) radicals are also investigated. The effects of these updates are compared against new high-pressure shock tube and rapid compression machine ignition delay measurements. It is shown that rate constant modifications are required to improve agreement between kinetic modeling simulations and experimental data. We further demonstrate the ability to optimize the kinetic model using both manual and automated techniques for rate parameter tunings to improve agreement with the measured ignition delay time data. Finally, additional low temperature chain branching reaction pathways are shown to improve the model’s performance. The present approach to model development provides better performance across extended operating conditions while also strengthening the fundamental basis of the model.

  18. Modeling Ignition of a Heptane Isomer: Improved Thermodynamics, Reaction Pathways, Kinetic, and Rate Rule Optimizations for 2-Methylhexane

    KAUST Repository

    Mohamed, Samah

    2016-03-21

    Accurate chemical kinetic combustion models of lightly branched alkanes (e.g., 2-methylalkanes) are important to investigate the combustion behavior of real fuels. Improving the fidelity of existing kinetic models is a necessity, as new experiments and advanced theories show inaccuracies in certain portions of the models. This study focuses on updating thermodynamic data and the kinetic reaction mechanism for a gasoline surrogate component, 2-methylhexane, based on recently published thermodynamic group values and rate rules derived from quantum calculations and experiments. Alternative pathways for the isomerization of peroxy-alkylhydroperoxide (OOQOOH) radicals are also investigated. The effects of these updates are compared against new high-pressure shock tube and rapid compression machine ignition delay measurements. It is shown that rate constant modifications are required to improve agreement between kinetic modeling simulations and experimental data. We further demonstrate the ability to optimize the kinetic model using both manual and automated techniques for rate parameter tunings to improve agreement with the measured ignition delay time data. Finally, additional low temperature chain branching reaction pathways are shown to improve the model’s performance. The present approach to model development provides better performance across extended operating conditions while also strengthening the fundamental basis of the model.

  19. A combined high-temperature experimental and theoretical kinetic study of the reaction of dimethyl carbonate with OH radicals

    KAUST Repository

    Khaled, Fathi; Giri, Binod; Szőri, Milá n; Mai, Tam V.-T.; Huynh, Lam K.; Farooq, Aamir

    2017-01-01

    The reaction kinetics of dimethyl carbonate (DMC) and OH radicals were investigated behind reflected shock waves over the temperature range of 872-1295 K and at pressures near 1.5 atm. Reaction progress was monitored by detecting OH radicals at 306.69 nm using a UV laser absorption technique. The rate coefficients for the reaction of DMC with OH radicals were extracted using a detailed kinetic model developed by Glaude et al. (Proc. Combust. Inst. 2005, 30(1), 1111-1118). The experimental rate coefficients can be expressed in Arrhenius form as: kexpt'l = 5.15 × 10(13) exp(-2710.2/T) cm(3) mol(-1) s(-1). To explore the detailed chemistry of the DMC + OH reaction system, theoretical kinetic analyses were performed using high-level ab initio and master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) calculations. Geometry optimization and frequency calculations were carried out at the second-order Møller-Plesset (MP2) perturbation level of theory using Dunning's augmented correlation consistent-polarized valence double-ζ basis set (aug-cc-pVDZ). The energy was extrapolated to the complete basis set using single point calculations performed at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory. For comparison purposes, additional ab initio calculations were also carried out using composite methods such as CBS-QB3, CBS-APNO, G3 and G4. Our calculations revealed that the H-abstraction reaction of DMC by OH radicals proceeds via an addition elimination mechanism in an overall exothermic process, eventually forming dimethyl carbonate radicals and H2O. Theoretical rate coefficients were found to be in excellent agreement with those determined experimentally. Rate coefficients for the DMC + OH reaction were combined with literature rate coefficients of four straight chain methyl ester + OH reactions to extract site-specific rates of H-abstraction from methyl esters by OH radicals.

  20. Kinetic and Mechanistic Study of the pH-Dependent Activation (Epoxidation) of Prodrug Treosulfan Including the Reaction Inhibition in a Borate Buffer.

    Science.gov (United States)

    Romański, Michał; Ratajczak, Whitney; Główka, Franciszek

    2017-07-01

    A prodrug treosulfan (T) undergoes a pH-dependent activation to epoxide derivatives. The process seems to involve an intramolecular Williamson reaction (IWR) but clear kinetic evidence is lacking. Moreover, a cis-diol system present in the T structure is expected to promote complexation with boric acid. As a result, the prodrug epoxidation would be inhibited; however, this phenomenon has not been investigated. In this article, the effect of pH on the kinetics of T conversion to its monoepoxide was studied from a mechanistic point of view. Also, the influence of boric acid on the reaction kinetics was examined. The rate constants observed for the activation of T (k obs ) in acetate, phosphate, and carbonate buffers satisfied the equation logk obs  = -7.48 + 0.96 pH. The reaction was inhibited in the excess of boric acid over T, and the k obs decreased with increasing borate buffer concentration. The experimental results were consistent with the inhibition model that included the formation of a tetrahedral, anionic T-boric acid monoester. To conclude, in nonborate buffers, the T activation to (2S,3S)-1,2-epoxybutane-3,4-diol 4-methanesulfonate follows IWR mechanism. A borate buffer changes the reaction kinetics and complicates kinetic analysis. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

  1. Chemical kinetics and reaction dynamics

    CERN Document Server

    Houston, Paul L

    2006-01-01

    This text teaches the principles underlying modern chemical kinetics in a clear, direct fashion, using several examples to enhance basic understanding. It features solutions to selected problems, with separate sections and appendices that cover more technical applications.Each chapter is self-contained and features an introduction that identifies its basic goals, their significance, and a general plan for their achievement. This text's important aims are to demonstrate that the basic kinetic principles are essential to the solution of modern chemical problems, and to show how the underlying qu

  2. Unravelling the kinetics of the formation of acrylamide in the Maillard reaction of fructose and asparagine by multiresponse modelling

    NARCIS (Netherlands)

    Knol, J.J.; Linssen, J.P.H.; Boekel, van M.A.J.S.

    2010-01-01

    A kinetic model for the formation of acrylamide in a fructose–asparagine reaction system at initial pH 5.5 is proposed, based on an approach called multiresponse kinetic modelling. The formation of acetic acid and formic acid from the degradation of fructose and its isomer glucose was included in

  3. Exploring the kinetic and thermodynamic aspects of four-electron electrochemical reactions: electrocatalysis of oxygen evolution by metal oxides and biological systems.

    Science.gov (United States)

    Wang, Vincent C-C

    2016-08-10

    Finding fundamental and general mechanisms for electrochemical reactions, such as the oxygen evolution reaction (OER) from water and reduction of CO2, plays vital roles in developing the desired electrocatalysts for facilitating solar fuel production. Recently, density functional theory (DFT) calculations have shown that there is a universal scaling relation of adsorption energy between key intermediate species, HO(ad) and HOO(ad), on the surface of metal oxides as OER electrocatalysts. In this paper, a kinetic and thermodynamic model for the four-electron electrochemical reaction based on previous OER mechanisms proposed by DFT calculations is developed to further investigate the electrocatalytic properties over a wide range of metal oxides and photosystem II. The OER activity of metal oxides (i.e. electrocatalytic current) calculated from the DFT-calculated equilibrium potentials with kinetic properties, such as the rate constants for interfacial electron transfer and catalytic turnover, can lead to a volcano-shaped trend that agrees with the results observed in experiments. In addition, the kinetic aspects of the impact on the electrocatalysts are evaluated. Finally, comparing the results of metal oxides and photosystem II, and fitting experimental voltammograms give further insights into kinetic and thermodynamic roles. Here, the general guidelines for designing OER electrocatalysts with unified kinetic and thermodynamic properties are presented.

  4. A Microscale Approach to Chemical Kinetics in the General Chemistry Laboratory: The Potassium Iodide Hydrogen Peroxide Iodine-Clock Reaction

    Science.gov (United States)

    Sattsangi, Prem D.

    2011-01-01

    A microscale laboratory for teaching chemical kinetics utilizing the iodine clock reaction is described. Plastic pipets, 3 mL volume, are used to store and deliver precise drops of reagents and the reaction is run in a 24 well plastic tray using a total 60 drops of reagents. With this procedure, students determine the rate of reaction and the…

  5. Role of interfacial defect creation-annihilation processes at grain boundaries on the diffusional creep of polycrystalline alumina

    International Nuclear Information System (INIS)

    Ikuma, Y.; Gordon, R.S.

    1981-01-01

    It is generally assumed in the diffusional creep of a polycrystalline solid that grain boundaries act as perfect sources and sinks for lattice defects. However, if this assumption is not valid, then diffusional creep can become rate limited by interfacial defect reactions at grain boundaries. Steady state diffusional creep data will be presented at 1450 to 1500 0 C for polycrystalline alumina doped with Ti and a Mg-Ti co-dopant, which are consistent with interfacial controlled kinetics over an intermediate grain size range. A new type of creep deformation map will be presented which reveals the range of grain sizes and impurity concentrations over which interfacial defect creation and/or annihilation processes are important in the steady state creep of polycrystalline alumina

  6. On the graph and systems analysis of reversible chemical reaction networks with mass action kinetics

    NARCIS (Netherlands)

    Rao, Shodhan; Jayawardhana, Bayu; Schaft, Arjan van der

    2012-01-01

    Motivated by the recent progresses on the interplay between the graph theory and systems theory, we revisit the analysis of reversible chemical reaction networks described by mass action kinetics by reformulating it using the graph knowledge of the underlying networks. Based on this formulation, we

  7. Reaction kinetic model of the surface-mediated formation of PCDD/F from pyrolysis of 2-chlorophenol on a CuP/Silica suface

    Energy Technology Data Exchange (ETDEWEB)

    Lomnicki, S.; Khachatryan, L.; Dellinger, B. [Louisiana State Univ., Baton Rouge (United States). Dept. of Chemistry

    2004-09-15

    One of the major challenges in developing predictive models of the surface mediated pollutant formation and fuel combustion is the construction of reliable reaction kinetic mechanisms and models. While the homogeneous, gas-phase chemistry of various light fuels such as hydrogen and methane is relatively well-known large uncertainties exist in the reaction paths of surface mediated reaction mechanisms for even these very simple species. To date, no detailed kinetic consideration of the surface mechanisms of formation of complex organics such as PCDD/F have been developed. In addition to the complexity of the mechanism, a major difficulty is the lack of reaction kinetic parameters (pre-exponential factor and activation energy) of surface reactions, Consequently, numerical studies of the surface-mediated formation of PCDD/F have often been incorporated only a few reactions. We report the development of a numerical multiple-step surface model based on experimental data of surface mediated (5% CuO/SiO2) conversion of 2-monochlorphenol (2-MCP) to PCDD/F under pyrolytic or oxidative conditions. A reaction kinetic model of the catalytic conversion of 2-MCP on the copper oxide catalyst under pyrolytic conditions was developed based on a detailed multistep surface reaction mechanism developed in our laboratory. The performance of the chemical model is assessed by comparing the numerical predictions with experimental measurements. SURFACE CHEMKIN (version 3.7.1) software was used for modeling. Our results confirm the validity of previously published mechanism of the reaction and provides new insight concerning the formation of PCDD/F formation in combustion processes. This model successfully explains the high yields of PCDD/F at low temperatures that cannot be explained using a purely gas-phase mode.

  8. The kinetics of dolomite reaction rim growth under isostatic and non-isostatic pressure conditions

    Science.gov (United States)

    Helpa, V.; Rybacki, E.; Morales, L. G.; Abart, R.; Dresen, G. H.

    2013-12-01

    During burial and exhumation, rocks are simultaneously exposed to metamorphic reactions and tectonic stresses. Therefore, the reaction rate of newly formed minerals may depend on chemical and mechanical driving forces. Here, we investigate the reaction kinetics of dolomite (CaMg[CO3]2) rim growth by solid-state reactions experiments on oriented calcite (CaCO3) and magnesite (MgCO3) single crystals under isostatic and non-isostatic pressure conditions. Cylindrical samples of 3-5 mm length and 7 mm diameter were drilled and polished perpendicular to the rhombohedral cleavage planes of natural clear crystals. The tests were performed using a Paterson-type deformation apparatus at P = 400 MPa confining pressure, temperatures, T, between 750 and 850°C, and reaction durations, t, of 2 - 146 h to calculate the kinetic parameters of dolomite rim growth under isostatic stress conditions. For non-isostatic reaction experiments we applied in addition differential stresses, σ, up to 40 MPa perpendicular to the contact interface at T = 750°C for 4 - 171 h duration, initiating minor inelastic deformation of calcite. The thickness of the resulting dolomite reaction rims increases linearly with the square root of time, indicating a diffusion-controlled reaction. The rims consist of two different textural domains. Granular dolomite grains (≈ 2 -5 μm grain size) form next to calcite and elongated palisade-shaped grains (1-6 μm diameter) grow perpendicular to the magnesite interface. Texture measurements with the electron backscatter diffraction technique indicate that the orientations of dolomite grains are mainly influenced by the orientation of the calcite educt crystal, in particular in the granular rim. To some extent, the texture of dolomite palisades is also influenced by the orientation of magnesite. The thickness of the two individual layers increases with temperature. At 400 MPa isostatic pressure, T = 750°C and t = 29 hours, a 5 μm thick granular dolomite layer

  9. Kinetic Modeling of the Reaction Rate for Quartz and Carbon Pellet

    Science.gov (United States)

    Li, Fei; Tangstad, Merete

    2018-04-01

    Kinetic modeling of quartz and carbon pellet at temperatures of 1898 K, 1923 K, and 1948 K (1625 °C, 1650 °C, and 1675 °C) was investigated in this study. The carbon materials used were charcoal, coke, coal, and preheated coal. The overall SiC producing reaction can be described by the reaction SiO2 + 3C = SiC + 2CO. In the SiC-producing step, the reaction rate of quartz and carbon pellet can be expressed as {d{ pct}}/dt = ( {1 - 0.40 × X_{fix - C}^{ - 0.86} × FC × {pct}} ) × A × \\exp ( { - E/{{RT}}} ) The carbon factor F C was used to describe the influence of different carbon materials that effect the gas-solid interface reaction. For charcoal, coke, coal, and preheated coal, the F C values were 0.83, 0.80, 0.94, and 0.83, respectively. The pre-exponential factor A values for the preceding four carbon materials were 1.06 × 1016 min-1, 4.21 × 1015 min-1, 3.85 × 109 min-1, and 1.00 × 1025 min-1, respectively. The activation energies E for the SiC-producing step were 570, 563, 336, and 913 kJ/mole for charcoal, coke, coal, and preheated coal pellets, respectively.

  10. Noise-induced modulation of the relaxation kinetics around a non-equilibrium steady state of non-linear chemical reaction networks.

    Science.gov (United States)

    Ramaswamy, Rajesh; Sbalzarini, Ivo F; González-Segredo, Nélido

    2011-01-28

    Stochastic effects from correlated noise non-trivially modulate the kinetics of non-linear chemical reaction networks. This is especially important in systems where reactions are confined to small volumes and reactants are delivered in bursts. We characterise how the two noise sources confinement and burst modulate the relaxation kinetics of a non-linear reaction network around a non-equilibrium steady state. We find that the lifetimes of species change with burst input and confinement. Confinement increases the lifetimes of all species that are involved in any non-linear reaction as a reactant. Burst monotonically increases or decreases lifetimes. Competition between burst-induced and confinement-induced modulation may hence lead to a non-monotonic modulation. We quantify lifetime as the integral of the time autocorrelation function (ACF) of concentration fluctuations around a non-equilibrium steady state of the reaction network. Furthermore, we look at the first and second derivatives of the ACF, each of which is affected in opposite ways by burst and confinement. This allows discriminating between these two noise sources. We analytically derive the ACF from the linear Fokker-Planck approximation of the chemical master equation in order to establish a baseline for the burst-induced modulation at low confinement. Effects of higher confinement are then studied using a partial-propensity stochastic simulation algorithm. The results presented here may help understand the mechanisms that deviate stochastic kinetics from its deterministic counterpart. In addition, they may be instrumental when using fluorescence-lifetime imaging microscopy (FLIM) or fluorescence-correlation spectroscopy (FCS) to measure confinement and burst in systems with known reaction rates, or, alternatively, to correct for the effects of confinement and burst when experimentally measuring reaction rates.

  11. A robust methodology for kinetic model parameter estimation for biocatalytic reactions

    DEFF Research Database (Denmark)

    Al-Haque, Naweed; Andrade Santacoloma, Paloma de Gracia; Lima Afonso Neto, Watson

    2012-01-01

    lead to globally optimized parameter values. In this article, a robust methodology to estimate parameters for biocatalytic reaction kinetic expressions is proposed. The methodology determines the parameters in a systematic manner by exploiting the best features of several of the current approaches...... parameters, which are strongly correlated with each other. State-of-the-art methodologies such as nonlinear regression (using progress curves) or graphical analysis (using initial rate data, for example, the Lineweaver-Burke plot, Hanes plot or Dixon plot) often incorporate errors in the estimates and rarely...

  12. Kinetics of reaction of 1,10- decanedioland dimeric fatty acid C36

    International Nuclear Information System (INIS)

    Falah, A.

    2013-01-01

    Kinetic studies were carried out on the reaction between 1,10- Decanedioland dimeric fatty acid C 3 6 in melt phase. The reaction was performed at 140, 150, 160, 170, and 185 o C and followed by determining the acid value of the product. The polyesterfication reaction was found to be of overall second order with an activation energy of 39,91kj/mol up to (50, 44, 55,42, 63)% conversion at (140, 150, 160, 170, 185) o C and overall third order with an activation energy of 71.17 k j/ mol above (50, 44, 55, 42, 63)% conversion at (140, 150, 160, 170, 185) o C. The Degree of Polymerization, number average molecular weight and weight average molecular weight have been calculated during different times, the relationships between Degree of Polymerization, number average molecular weight, weight average molecular weight and the times is linear until, (50, 44, 55, 42, 63)%conversion at (140, 150, 160, 170, 185) o C. (author)

  13. A kinetic Monte Carlo study on the role of defects and detachment in the formation and growth of In chains on Si(100)

    International Nuclear Information System (INIS)

    Albao, Marvin A; Chuang, F-C; Evans, J W

    2009-01-01

    Deposition on a Si(100) surface and subsequent self-assembly of In atoms into one-dimensional (1D) atomic chains at room temperature is investigated via kinetic Monte Carlo simulation of a suitable atomistic model. Model development is guided by recent experimental observations in which 1D In chains nucleate effectively exclusively at C-type defects, although In atoms can detach from chains. We find that a monotonically decreasing form of the scaled island size distribution (ISD) is consistent with a high defect density which facilitates persistent chain nucleation even at relatively high coverages. The predominance of heterogeneous nucleation may be attributed to several factors including low surface diffusion barriers, a high defect density, and relatively weak In-In binding.

  14. Application of adjustable pulse lasers to studying rapid reaction kinetics of excited lanthanide complexing

    Energy Technology Data Exchange (ETDEWEB)

    Gruzdev, V.P. (Gosudarstvennyj Opticheskij Inst., Leningrad (USSR))

    1983-12-01

    Using some europium (3) ion complexes new possibilities to be opened by application of adjustable pulse lasers for studying rapid reactions of electron-excited metal ion complexing are demonstrated. The 6Zh rhodamine pulse laser is used as a source of nonequilibrium photoexcitation of an array of Eu/sup 3 +/ complexes in the luminescent kinetic spectroscopy method. The following results are obtained: for the first time the rate of reaction of acetate ion substitution for water molecules of an excited (/sup 5/D/sub 0/) ion of Eu/sup 3 +/ was measured to be (0.7+-0.2)x10/sup 7/ s/sup -1/; using direct experiments the lower limit for the rate of transition of one isomeric form of the excited Eu x EDTA complex into another one in an aqueous solution is determined to be 5x10/sup 5/ s/sup -1/ at 295 K; the kinetics of the excitation energy migration beteen aqueous solvates of Eu/sup 3 +/ and EuxEDTA complexes is investigated.

  15. Golden rule kinetics of transfer reactions in condensed phase: the microscopic model of electron transfer reactions in disordered solid matrices.

    Science.gov (United States)

    Basilevsky, M V; Odinokov, A V; Titov, S V; Mitina, E A

    2013-12-21

    The algorithm for a theoretical calculation of transfer reaction rates for light quantum particles (i.e., the electron and H-atom transfers) in non-polar solid matrices is formulated and justified. The mechanism postulated involves a local mode (an either intra- or inter-molecular one) serving as a mediator which accomplishes the energy exchange between the reacting high-frequency quantum mode and the phonon modes belonging to the environment. This approach uses as a background the Fermi golden rule beyond the usually applied spin-boson approximation. The dynamical treatment rests on the one-dimensional version of the standard quantum relaxation equation for the reduced density matrix, which describes the frequency fluctuation spectrum for the local mode under consideration. The temperature dependence of a reaction rate is controlled by the dimensionless parameter ξ0 = ℏω0/k(B)T where ω0 is the frequency of the local mode and T is the temperature. The realization of the computational scheme is different for the high/intermediate (ξ0 regime, the Redfield approximation to the solution of the relaxation equation proved to be sufficient and efficient in practical applications. The study of the essentially quantum-mechanical low-temperature kinetic regime in its asymptotic limit requires the implementation of the exact relaxation equation. The coherent mechanism providing a non-vanishing reaction rate has been revealed when T → 0. An accurate computational methodology for the cross-over kinetic regime needs a further elaboration. The original model of the hopping mechanism for electronic conduction in photosensitive organic materials is considered, based on the above techniques. The electron transfer (ET) in active centers of such systems proceeds via local intra- and intermolecular modes. The active modes, as a rule, operate beyond the kinetic regimes, which are usually postulated in the existing theories of the ET. Our alternative dynamic ET model for local

  16. A Kinetic Study of the Gas-Phase Reaction of OH with Br2

    Science.gov (United States)

    Bryukov, Mikhail G.; Dellinger, Barry; Knyazev, Vadim D.

    2011-01-01

    An experimental, temperature-dependent kinetic study of the gas-phase reaction of the hydroxyl radical with molecular bromine (reaction 1) has been performed using a pulsed laser photolysis/pulsed-laser-induced fluorescence technique over a wide temperature range of 297 – 766 K, and at pressures between 6.68 and 40.29 kPa of helium. The experimental rate coefficients for reaction 1 demonstrate no correlation with pressure and exhibit a negative temperature dependence with a slight negative curvature in the Arrhenius plot. A non-linear least-squares fit with two floating parameters of the temperature dependent k1(T) data set using an equation of the form k1(T) = ATn yields the recommended expression k1(T) = 1.85×10−9T − 0.66 cm3 molecule−1 s−1 for the temperature dependence of the reaction 1 rate coefficient. The potential energy surface (PES) of reaction 1 was investigated using quantum chemistry methods. The reaction proceeds through formation of a weakly bound OH···Br2 complex and a PES saddle point with an energy below that of the reactants. Temperature dependence of the reaction rate coefficient was modeled using the RRKM method on the basis of the calculated PES. PMID:16854030

  17. Synchronous parallel kinetic Monte Carlo for continuum diffusion-reaction systems

    International Nuclear Information System (INIS)

    Martinez, E.; Marian, J.; Kalos, M.H.; Perlado, J.M.

    2008-01-01

    A novel parallel kinetic Monte Carlo (kMC) algorithm formulated on the basis of perfect time synchronicity is presented. The algorithm is intended as a generalization of the standard n-fold kMC method, and is trivially implemented in parallel architectures. In its present form, the algorithm is not rigorous in the sense that boundary conflicts are ignored. We demonstrate, however, that, in their absence, or if they were correctly accounted for, our algorithm solves the same master equation as the serial method. We test the validity and parallel performance of the method by solving several pure diffusion problems (i.e. with no particle interactions) with known analytical solution. We also study diffusion-reaction systems with known asymptotic behavior and find that, for large systems with interaction radii smaller than the typical diffusion length, boundary conflicts are negligible and do not affect the global kinetic evolution, which is seen to agree with the expected analytical behavior. Our method is a controlled approximation in the sense that the error incurred by ignoring boundary conflicts can be quantified intrinsically, during the course of a simulation, and decreased arbitrarily (controlled) by modifying a few problem-dependent simulation parameters

  18. Fast and calibration free determination of first order reaction kinetics in API synthesis using in-situ ATR-FTIR.

    Science.gov (United States)

    Rehbein, Moritz C; Husmann, Sascha; Lechner, Christian; Kunick, Conrad; Scholl, Stephan

    2018-05-01

    In early stages of drug development only sparse amounts of the key substances are available, which is problematic for the determination of important process data like reaction kinetics. Therefore, it is important to perform experiments as economically as possible, especially in regards to limiting compounds. Here we demonstrate the use of a temperature step experiment enabling the determination of complete reaction kinetics in a single non-isothermal experiment. In contrast to the traditionally used HPLC, the method takes advantage of the high measuring rate and the low amount of labor involved in using in-situ ATR-FTIR to determine time-dependent concentration-equivalent data. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Material Balance And Reaction Kinetics Modeling For Penex Isomerization Process In Daura Refinery

    Directory of Open Access Journals (Sweden)

    Hamadi Adel Sharif

    2017-01-01

    Full Text Available Penex Deisohexanizer isomerization of light straight run naphtha is a significant process for petroleum refining and proved to be effective technology to produce gasoline components with a high octane number. Modeling of the chemical kinetic reactions is an important tool because it is a better tool for optimization of the experimental data into parameters used for industrial reactors. The present study deals on the isomerization process in Daura refinery. Material balance calculations were done mathematically on the unit for the kinetics prediction purpose. A kinetic mathematical model was derived for the prediction rate constants K1 and K2 and activation energy Ea at operating temperatures range 120-180°C. According to the model, the results show that with increasing of temperature leads to increased K1 directly, where the K2 values proportional inversely. The activation energy results show that Ea1(nC6

  20. Hybrid quantum and classical methods for computing kinetic isotope effects of chemical reactions in solutions and in enzymes.

    Science.gov (United States)

    Gao, Jiali; Major, Dan T; Fan, Yao; Lin, Yen-Lin; Ma, Shuhua; Wong, Kin-Yiu

    2008-01-01

    A method for incorporating quantum mechanics into enzyme kinetics modeling is presented. Three aspects are emphasized: 1) combined quantum mechanical and molecular mechanical methods are used to represent the potential energy surface for modeling bond forming and breaking processes, 2) instantaneous normal mode analyses are used to incorporate quantum vibrational free energies to the classical potential of mean force, and 3) multidimensional tunneling methods are used to estimate quantum effects on the reaction coordinate motion. Centroid path integral simulations are described to make quantum corrections to the classical potential of mean force. In this method, the nuclear quantum vibrational and tunneling contributions are not separable. An integrated centroid path integral-free energy perturbation and umbrella sampling (PI-FEP/UM) method along with a bisection sampling procedure was summarized, which provides an accurate, easily convergent method for computing kinetic isotope effects for chemical reactions in solution and in enzymes. In the ensemble-averaged variational transition state theory with multidimensional tunneling (EA-VTST/MT), these three aspects of quantum mechanical effects can be individually treated, providing useful insights into the mechanism of enzymatic reactions. These methods are illustrated by applications to a model process in the gas phase, the decarboxylation reaction of N-methyl picolinate in water, and the proton abstraction and reprotonation process catalyzed by alanine racemase. These examples show that the incorporation of quantum mechanical effects is essential for enzyme kinetics simulations.

  1. Deduction of kinetic mechanism in multisubstrate enzyme reactions from tritium isotope effects. Application to dopamine beta-hydroxylase

    International Nuclear Information System (INIS)

    Klinman, J.P.; Humphries, H.; Voet, J.G.

    1980-01-01

    Primary tritium isotope effects have been measured for the hydroxylation of [2-3H] dopamine catalyzed by dopamine beta-hydroxylase. Experimental values vary from 8.8 +/- 1.4 at 0.02 mM oxygen to 4.1 +/- 0.6 at 1.0 mM oxygen. It is shown that the observed dependence of the isotope effect on oxygen concentration provides unequivocal evidence for a kinetically significant dissociation of both dopamine and oxygen from enzyme, ternary complex. This approach, which is applicable to any multisubstrate enzyme characterized by detectable kinetic isotope effects, provides an alternate to classical methods for the elucidation of kinetic order in enzyme-catalyzed reactions

  2. Thermodynamics of axial substitution and kinetics of reactions with amino acids for the paddlewheel complex tetrakis(acetato)chloridodiruthenium(II,III).

    Science.gov (United States)

    Santos, Rodrigo L S R; van Eldik, Rudi; de Oliveira Silva, Denise

    2012-06-18

    The known paddlewheel, tetrakis(acetato)chloridodiruthenium(II,III), offers a versatile synthetic route to a novel class of antitumor diruthenium(II,III) metallo drugs, where the equatorial ligands are nonsteroidal anti-inflammatory carboxylates. This complex was studied here as a soluble starting prototype model for antitumor analogues to elucidate the reactivity of the [Ru(2)(CH(3)COO)(4)](+) framework. Thermodynamic studies on equilibration reactions for axial substitution of water by chloride and kinetic studies on reactions of the diaqua complexes with the amino acids glycine, cysteine, histidine, and tryptophan were performed. The standard thermodynamic reaction parameters ΔH°, ΔS°, and ΔV° were determined and showed that both of the sequential axial substitution reactions are enthalpy driven. Kinetic rate laws and rate constants were determined for the axial substitution reactions of coordinated water by the amino acids that gave the corresponding aqua(amino acid)-Ru(2) substituted species. The results revealed that the [Ru(2)(CH(3)COO)(4)](+) paddlewheel framework remained stable during the axial ligand substitution reactions and was also mostly preserved in the presence of the amino acids.

  3. HTP kinetics studies on isolated elementary combustion reactions over wide temperature ranges

    Energy Technology Data Exchange (ETDEWEB)

    Fontijn, A.; Adusei, G.Y.; Hranisavlevic, J.; Bajaj, P.N. [Rensselaer Polytechnic Institute, Troy, NY (United States)

    1993-12-01

    The goals of this project are to provide accurate data on the temperature dependence of the kinetics of elementary combustion reactions, (i) for use by combustion modelers, and (ii) to gain a better fundamental understanding of, and hence predictive ability for, the chemistry involved. Experimental measurements are made mainly by using the pseudo-static HTP (high-temperature photochemistry) technique. While continuing rate coefficient measurements, further aspects of kinetics research are being explored. Thus, starting from the data obtained, a method for predicting the temperature dependence of rate coefficients of oxygen-atom olefin experiment and confirms the underlying mechanistic assumptions. Mechanistic information of another sort, i.e. by product analysis, has recently become accessible with the inauguration of our heated flow tube mass spectrometer facility; early results are reported here. HTP experiments designed to lead to measurements of product channels by resonance fluorescence have started.

  4. Kinetic isotope effects in the CH4 + H→CH3 + H2 system. Predictions of the LMR six-body potential-energy reaction hypersurface

    International Nuclear Information System (INIS)

    Marriott, T.D.

    1976-01-01

    Scope of Study: The purpose of this study was two-fold. First, it served to test, in part, the usefulness of the LMR six-body potential-energy surface (LMR-PES) for transition-state theory predictions of the kinetic isotope effects for both the forward and reverse reactions of CH 4 + H reversible CH 3 + H 2 . In this regard the agreement between experimental and theoretical isotope effects, assuming the former to be accurate, provides information about the accuracy of the curvature of the potential energy surface for motion both parallel and perpendicular to the reaction coordinate. Second, these isotope effects were used to assess the validity of a number of qualitative and semi-quantitative interpretations of kinetic isotope effects developed in physical organic chemistry with regard to this reaction system. The force constants and geometries obtained numerically from the LMR-PES were found to produce reasonable harmonic approximations to the reactant normal mode frequencies. Neglecting tunneling, the LMR-PES reasonably reproduces the experimental k/sub H//k/sub D/ values for the reactions CH 4 + H(D), CH 3 + HD(DH) and CD 2 + HD(DH). Since previous theoretical treatments of primary deuterium kinetic isotope effects have neglected the bending normal mode frequencies, a semi-quantitative study of the effect of neglecting bending frequencies on the VP, EXC, and ZPE elements as well as the transition-state theory kinetic isotope effects was performed. The Swain-Schaad relationship between primary deuterium and tritium kinetic isotope effects was shown to hold to a reasonable degree of accuracy for the LMR-PES reaction system. A relationship between 13-carbon and 14-carbon kinetic isotope effects similar to the Swain-Schaad relationship was derived

  5. 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)

  6. Heterogeneous reaction of particulate chlorpyrifos with NO3 radicals: Products, pathways, and kinetics

    Science.gov (United States)

    Li, Nana; Zhang, Peng; Yang, Bo; Shu, Jinian; Wang, Youfeng; Sun, Wanqi

    2014-08-01

    Chlorpyrifos is a typical chlorinated organophosphorus pesticide. The heterogeneous reaction of chlorpyrifos particles with NO3 radicals was investigated using a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS) and a real-time atmospheric gas analysis mass spectrometer. Chlorpyrifos oxon, 3,5,6-trichloro-2-pyridinol, O,O-diethyl O-hydrogen phosphorothioate, O,O-diethyl ester thiophosphoric acid, diethyl hydrogen phosphate and a phosphinyl disulfide compound were identified as the main degradation products. The heterogeneous reaction pathways were proposed and their kinetic processes were investigated via a mixed-phase relative rate method. The observed effective rate constant is 3.4 ± 0.2 × 10-12 cm3 molecule-1 s-1.

  7. Noise-induced modulation of the relaxation kinetics around a non-equilibrium steady state of non-linear chemical reaction networks.

    Directory of Open Access Journals (Sweden)

    Rajesh Ramaswamy

    2011-01-01

    Full Text Available Stochastic effects from correlated noise non-trivially modulate the kinetics of non-linear chemical reaction networks. This is especially important in systems where reactions are confined to small volumes and reactants are delivered in bursts. We characterise how the two noise sources confinement and burst modulate the relaxation kinetics of a non-linear reaction network around a non-equilibrium steady state. We find that the lifetimes of species change with burst input and confinement. Confinement increases the lifetimes of all species that are involved in any non-linear reaction as a reactant. Burst monotonically increases or decreases lifetimes. Competition between burst-induced and confinement-induced modulation may hence lead to a non-monotonic modulation. We quantify lifetime as the integral of the time autocorrelation function (ACF of concentration fluctuations around a non-equilibrium steady state of the reaction network. Furthermore, we look at the first and second derivatives of the ACF, each of which is affected in opposite ways by burst and confinement. This allows discriminating between these two noise sources. We analytically derive the ACF from the linear Fokker-Planck approximation of the chemical master equation in order to establish a baseline for the burst-induced modulation at low confinement. Effects of higher confinement are then studied using a partial-propensity stochastic simulation algorithm. The results presented here may help understand the mechanisms that deviate stochastic kinetics from its deterministic counterpart. In addition, they may be instrumental when using fluorescence-lifetime imaging microscopy (FLIM or fluorescence-correlation spectroscopy (FCS to measure confinement and burst in systems with known reaction rates, or, alternatively, to correct for the effects of confinement and burst when experimentally measuring reaction rates.

  8. 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.

  9. Malonic acid concentration as a control parameter in the kinetic analysis of the Belousov-Zhabotinsky reaction under batch conditions.

    Science.gov (United States)

    Blagojević, Slavica M; Anić, Slobodan R; Cupić, Zeljko D; Pejić, Natasa D; Kolar-Anić, Ljiljana Z

    2008-11-28

    The influence of the initial malonic acid concentration [MA]0 (8.00 x 10(-3) sulfuric acid (1.00 mol dm(-3)) and cerium sulfate (2.50 x 10(-3) mol dm(-3)) on the dynamics and the kinetics of the Belousov-Zhabotinsky (BZ) reactions was examined under batch conditions at 30.0 degrees C. The kinetics of the BZ reaction was analyzed by the earlier proposed method convenient for the examinations of the oscillatory reactions. In the defined region of parameters where oscillograms with only large-amplitude relaxation oscillations appeared, the pseudo-first order of the overall malonic acid decomposition with a corresponding rate constant of 2.14 x 10(-2) min(-1) was established. The numerical results on the dynamics and kinetics of the BZ reaction, carried out by the known skeleton model including the Br2O species, were in good agreement with the experimental ones. The already found saddle node infinite period (SNIPER) bifurcation point in transition from a stable quasi-steady state to periodic orbits and vice versa is confirmed by both experimental and numerical investigations of the system under consideration. Namely, the large-amplitude relaxation oscillations with increasing periods between oscillations in approaching the bifurcation points at the beginning and the end of the oscillatory domain, together with excitability of the stable quasi-steady states in their vicinity are obtained.

  10. Interactions of nitrite with catalase: Enzyme activity and reaction kinetics studies.

    Science.gov (United States)

    Krych-Madej, Justyna; Gebicka, Lidia

    2017-06-01

    Catalase, a heme enzyme, which catalyzes decomposition of hydrogen peroxide to water and molecular oxygen, is one of the main enzymes of the antioxidant defense system of the cell. Nitrite, used as a food preservative has long been regarded as a harmful compound due to its ability to form carcinogenic nitrosamines. Recently, much evidence has been presented that nitrite plays a protective role as a nitric oxide donor under hypoxic conditions. In this work the effect of nitrite on the catalytic reactions of catalase was studied. Catalase was inhibited by nitrite, and this process was pH-dependent. IC 50 values varied from about 1μM at pH5.0 to about 150μM of nitrite at pH7.4. The presence of chloride significantly enhanced nitrite-induced catalase inhibition, in agreement with earlier observations. The kinetics of the reactions of nitrite with ferric catalase, its redox intermediate, Compound I, and catalase inactive form, Compound II, was also studied. Possible mechanisms of nitrite-induced catalase inhibition are analyzed and the biological consequences of the reactions of catalase with nitrite are discussed. Copyright © 2017 Elsevier Inc. All rights reserved.

  11. Kinetics of free radical decay reactions in lactic acid homo and copolymers irradiated to sterilization dose

    International Nuclear Information System (INIS)

    Kantoglu, O.; Ozbey, T.; Gueven, O.

    1995-01-01

    The kinetics of free radical decay reactions of poly(L-Lactic acid), poly(DL-Lactic acid) and random copolymer of lactic and glycolic acid have been investigated for decays taking place in air and in vacuum. The change in ESR lines of γ-irradiated polymers have been followed over a long time period. The decay has been found to follow neither simple first-order nor second-order kinetics. Various kinetic approaches including composite first or second-order mechanisms and diffusion-controlled first or second-order equations were determined to be also unsatisfactory. The decay of radicals in bulk irradiated lactic acid homo and copolymers was found to be best described when the second-order non-classical equation with time dependent rate constant approach was used. (Author)

  12. Experimental study of the reactions of limonene with OH and OD radicals: kinetics and products.

    Science.gov (United States)

    Braure, Tristan; Bedjanian, Yuri; Romanias, Manolis N; Morin, Julien; Riffault, Véronique; Tomas, Alexandre; Coddeville, Patrice

    2014-10-09

    The kinetics of the reactions of limonene with OH and OD radicals has been studied using a low-pressure flow tube reactor coupled with a quadrupole mass spectrometer: OH + C10H16 → products (1), OD + C10H16 → products (2). The rate constants of the title reactions were determined using four different approaches: either monitoring the kinetics of OH (OD) radicals or limonene consumption in excess of limonene or of the radicals, respectively (absolute method), and by the relative rate method using either the reaction OH (OD) + Br2 or OH (OD) + DMDS (dimethyl disulfide) as the reference one and following HOBr (DOBr) formation or DMDS and limonene consumption, respectively. As a result of the absolute and relative measurements, the overall rate coefficients, k1 = (3.0 ± 0.5) × 10(-11) exp((515 ± 50)/T) and k2 = (2.5 ± 0.6) × 10(-11) exp((575 ± 60)/T) cm(3) molecule(-1) s(-1), were determined at a pressure of 1 Torr of helium over the temperature ranges 220-360 and 233-353 K, respectively. k1 was found to be pressure independent over the range 0.5-5 Torr. There are two possible pathways for the reaction between OH (OD) and limonene: addition of the radical to one of the limonene double bonds (reactions 1a and 2a ) and abstraction of a hydrogen atom (reactions 1b and 2b ), resulting in the formation of H2O (HOD). Measurements of the HOD yield as a function of temperature led to the following branching ratio of the H atom abstraction channel: k2b/k2 = (0.07 ± 0.03) × exp((460 ± 140)/T) for T = (253-355) K.

  13. A kinetics database and scripts for PHREEQC

    Science.gov (United States)

    Hu, B.; Zhang, Y.; Teng, Y.; Zhu, C.

    2017-12-01

    Kinetics of geochemical reactions has been increasingly used in numerical models to simulate coupled flow, mass transport, and chemical reactions. However, the kinetic data are scattered in the literature. To assemble a kinetic dataset for a modeling project is an intimidating task for most. In order to facilitate the application of kinetics in geochemical modeling, we assembled kinetics parameters into a database for the geochemical simulation program, PHREEQC (version 3.0). Kinetics data were collected from the literature. Our database includes kinetic data for over 70 minerals. The rate equations are also programmed into scripts with the Basic language. Using the new kinetic database, we simulated reaction path during the albite dissolution process using various rate equations in the literature. The simulation results with three different rate equations gave difference reaction paths at different time scale. Another application involves a coupled reactive transport model simulating the advancement of an acid plume in an acid mine drainage site associated with Bear Creek Uranium tailings pond. Geochemical reactions including calcite, gypsum, and illite were simulated with PHREEQC using the new kinetic database. The simulation results successfully demonstrated the utility of new kinetic database.

  14. Effect of electron injection on defect reactions in irradiated silicon containing boron, carbon, and oxygen

    Science.gov (United States)

    Makarenko, L. F.; Lastovskii, S. B.; Yakushevich, H. S.; Moll, M.; Pintilie, I.

    2018-04-01

    Comparative studies employing Deep Level Transient Spectroscopy and C-V measurements have been performed on recombination-enhanced reactions between defects of interstitial type in boron doped silicon diodes irradiated with alpha-particles. It has been shown that self-interstitial related defects which are immobile even at room temperatures can be activated by very low forward currents at liquid nitrogen temperatures. Their activation is accompanied by the appearance of interstitial carbon atoms. It has been found that at rather high forward current densities which enhance BiOi complex disappearance, a retardation of Ci annealing takes place. Contrary to conventional thermal annealing of the interstitial boron-interstitial oxygen complex, the use of forward current injection helps to recover an essential part of charge carriers removed due to irradiation.

  15. Detailed Reaction Kinetics for CFD Modeling of Nuclear Fuel Pellet Coating for High Temperature Gas-Cooled Reactors

    International Nuclear Information System (INIS)

    Battaglia, Francine

    2008-01-01

    The research project was related to the Advanced Fuel Cycle Initiative and was in direct alignment with advancing knowledge in the area of Nuclear Fuel Development related to the use of TRISO fuels for high-temperature reactors. The importance of properly coating nuclear fuel pellets received a renewed interest for the safe production of nuclear power to help meet the energy requirements of the United States. High-temperature gas-cooled nuclear reactors use fuel in the form of coated uranium particles, and it is the coating process that was of importance to this project. The coating process requires four coating layers to retain radioactive fission products from escaping into the environment. The first layer consists of porous carbon and serves as a buffer layer to attenuate the fission and accommodate the fuel kernel swelling. The second (inner) layer is of pyrocarbon and provides protection from fission products and supports the third layer, which is silicon carbide. The final (outer) layer is also pyrocarbon and provides a bonding surface and protective barrier for the entire pellet. The coating procedures for the silicon carbide and the outer pyrocarbon layers require knowledge of the detailed kinetics of the reaction processes in the gas phase and at the surfaces where the particles interact with the reactor walls. The intent of this project was to acquire detailed information on the reaction kinetics for the chemical vapor deposition (CVD) of carbon and silicon carbine on uranium fuel pellets, including the location of transition state structures, evaluation of the associated activation energies, and the use of these activation energies in the prediction of reaction rate constants. After the detailed reaction kinetics were determined, the reactions were implemented and tested in a computational fluid dynamics model, MFIX. The intention was to find a reduced mechanism set to reduce the computational time for a simulation, while still providing accurate results

  16. Reaction kinetics and mechanisms of organosilicon fungicide flusilazole with sulfate and hydroxyl radicals.

    Science.gov (United States)

    Mercado, D Fabio; Bracco, Larisa L B; Arques, Antonio; Gonzalez, Mónica C; Caregnato, Paula

    2018-01-01

    Flusilazole is an organosilane fungicide used for treatments in agriculture and horticulture for control of diseases. The reaction kinetics and mechanism of flusilazole with sulfate and hydroxyl radicals were studied. The rate constant of the radicals with the fungicide were determined by laser flash photolysis of peroxodisulfate and hydrogen peroxide. The results were 2.0 × 10 9 s -1 M -1 for the reaction of the fungicide with HO and 4.6 × 10 8  s -1  M -1 for the same reaction with SO 4 - radicals. The absorption spectra of organic intermediates detected by laser flash photolysis of S 2 O 8 2- with flusilazole, were identified as α-aminoalkyl and siloxyl radicals and agree very well with those estimated employing the time-dependent density functional theory with explicit account for bulk solvent effects. In the continuous photolysis experiments, performed by photo-Fenton reaction of the fungicide, the main degradation products were: (bis(4-fluorophenyl)-hydroxy-methylsilane) and the non-toxic silicic acid, diethyl bis(trimethylsilyl) ester, in ten and twenty minutes of reaction, respectively. Copyright © 2017. Published by Elsevier Ltd.

  17. Calculations of radiation defect formation cross sections in reactor materials in (n,p) and (n,α) reactions

    International Nuclear Information System (INIS)

    Kupchishin, A.A.; Kupchishin, A.I.; Omarbekova, Zh.

    2001-01-01

    In the work an experimental data analysis by integral σ(E 1 ) and differential [dσ(E 1 ,E 2 )]/dE 2 neutron interaction cross sections with reactor materials with the secondary protons and alpha particles generation as well as with the primarily knock-on atoms production in such reactions are carried out. It is shown, that in the (n,p) and (n',α) reactions the recoil nuclei receive essential energy portion and they are the patriarchs for atom-atom cascades in the substance. Nuclear reactions with formation of the secondary α-particles and and recoil nuclei are considered. It is shown, that these reactions are effectively proceeding within neutrons energy range 0.3-15 MeV. The nuclear reactions kinematics of above mentioned processes is studied. Energy conservation law for these reaction is applied. Deferential cross section conservation and transformation law for radiation defect formation in the (n,α) reaction are considered as well

  18. A combined high-temperature experimental and theoretical kinetic study of the reaction of dimethyl carbonate with OH radicals

    KAUST Repository

    Khaled, Fathi

    2017-02-08

    The reaction kinetics of dimethyl carbonate (DMC) and OH radicals were investigated behind reflected shock waves over the temperature range of 872-1295 K and at pressures near 1.5 atm. Reaction progress was monitored by detecting OH radicals at 306.69 nm using a UV laser absorption technique. The rate coefficients for the reaction of DMC with OH radicals were extracted using a detailed kinetic model developed by Glaude et al. (Proc. Combust. Inst. 2005, 30(1), 1111-1118). The experimental rate coefficients can be expressed in Arrhenius form as: kexpt\\'l = 5.15 × 10(13) exp(-2710.2/T) cm(3) mol(-1) s(-1). To explore the detailed chemistry of the DMC + OH reaction system, theoretical kinetic analyses were performed using high-level ab initio and master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) calculations. Geometry optimization and frequency calculations were carried out at the second-order Møller-Plesset (MP2) perturbation level of theory using Dunning\\'s augmented correlation consistent-polarized valence double-ζ basis set (aug-cc-pVDZ). The energy was extrapolated to the complete basis set using single point calculations performed at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory. For comparison purposes, additional ab initio calculations were also carried out using composite methods such as CBS-QB3, CBS-APNO, G3 and G4. Our calculations revealed that the H-abstraction reaction of DMC by OH radicals proceeds via an addition elimination mechanism in an overall exothermic process, eventually forming dimethyl carbonate radicals and H2O. Theoretical rate coefficients were found to be in excellent agreement with those determined experimentally. Rate coefficients for the DMC + OH reaction were combined with literature rate coefficients of four straight chain methyl ester + OH reactions to extract site-specific rates of H-abstraction from methyl esters by OH radicals.

  19. Kinetics of two simultaneous second-order reactions occurring in different zones

    International Nuclear Information System (INIS)

    Dole, M.; Hsu, C.S.; Patel, V.M.; Patel, G.N.

    1975-01-01

    Equations have been derived for the case of free radicals recombining according to the second-order kinetics with or without diffusion control under the conditions that there are two simultaneous spatially separated recombination reactions but that only the overall free-radical concentration can be observed. The properties of these equations are discussed and methods for determining the three independent parameters in the first case and five in the second developed. The resulting equations have been applied to the interpretation of data obtained in studying the decay of allyl chain free radicals in irradiated extended chain crystalline polyethylene

  20. Introduction to chemical kinetics

    CERN Document Server

    Soustelle, Michel

    2013-01-01

    This book is a progressive presentation of kinetics of the chemical reactions. It provides complete coverage of the domain of chemical kinetics, which is necessary for the various future users in the fields of Chemistry, Physical Chemistry, Materials Science, Chemical Engineering, Macromolecular Chemistry and Combustion. It will help them to understand the most sophisticated knowledge of their future job area. Over 15 chapters, this book present the fundamentals of chemical kinetics, its relations with reaction mechanisms and kinetic properties. Two chapters are then devoted to experimental re

  1. Kinetics and selectivity of the oxidation of methylbenzenes in Co(III)-CH3COOH-CF3COOH solutions. Comparison with nitration and hydroxylation reactions

    International Nuclear Information System (INIS)

    Rudakov, E.S.; Lobachev, V.L.

    1989-01-01

    Data have been obtained concerning the kinetics, substrate selectivity, and kinetic isotope effect for the first stage in the oxidation of a series of arenes, from benzene to hexamethylbenzene, by Co(III) acetate in CH 3 COOH-CF 3 COOH (1.9 M) solutions at 25 degree C. A similarity was noted between substrate selectivity for reactions of alkylbenzenes with Co(III) and electrophilic nitration reactions, which occur via an electron transfer step. It was also found that substrate selectivity for these reactions differs significantly from that found for electrophilic hydroxylation reactions, which occur via an intermediate slow step involving σ-complex formation

  2. Ground reaction forces and knee kinetics during single and repeated badminton lunges.

    Science.gov (United States)

    Lam, Wing Kai; Ding, Rui; Qu, Yi

    2017-03-01

    Repeated movement (RM) lunge that frequently executed in badminton might be used for footwear evaluation. This study examined the influence of single movement (SM) and RM lunges on the ground reaction forces (GRFs) and knee kinetics during the braking phase of a badminton lunge step. Thirteen male university badminton players performed left-forward lunges in both SM and RM sessions. Force platform and motion capturing system were used to measure GRFs and knee kinetics variables. Paired t-test was performed to determine any significant differences between SM and RM lunges regarding mean and coefficient of variation (CV) in each variable. The kinetics results indicated that compared to SM lunges, the RM lunges had shorter contact time and generated smaller maximum loading rate of impact force, peak knee anterior-posterior force, and peak knee sagittal moment but generated larger peak horizontal resultant forces (Ps < 0.05). Additionally, the RM lunges had lower CV for peak knee medial-lateral and vertical forces (Ps < 0.05). These results suggested that the RM testing protocols had a distinct loading response and adaptation pattern during lunge and that the RM protocol showed higher within-trial reliability, which may be beneficial for the knee joint loading evaluation under different interventions.

  3. Full-dimensional analytical potential energy surface describing the gas-phase Cl + C2H6 reaction and kinetics study of rate constants and kinetic isotope effects.

    Science.gov (United States)

    Rangel, Cipriano; Espinosa-Garcia, Joaquin

    2018-02-07

    Within the Born-Oppenheimer approximation a full-dimensional analytical potential energy surface, PES-2017, was developed for the gas-phase hydrogen abstraction reaction between the chlorine atom and ethane, which is a nine body system. This surface presents a valence-bond/molecular mechanics functional form dependent on 60 parameters and is fitted to high-level ab initio calculations. This reaction presents little exothermicity, -2.30 kcal mol -1 , with a low height barrier, 2.44 kcal mol -1 , and intermediate complexes in the entrance and exit channels. We found that the energetic description was strongly dependent on the ab initio level used and it presented a very flat topology in the entrance channel, which represents a theoretical challenge in the fitting process. In general, PES-2017 reproduces the ab initio information used as input, which is merely a test of self-consistency. As a first test of the quality of the PES-2017, a theoretical kinetics study was performed in the temperature range 200-1400 K using two approaches, i.e. the variational transition-state theory and quasi-classical trajectory calculations, with spin-orbit effects. The rate constants show reasonable agreement with experiments in the whole temperature range, with the largest differences at the lowest temperatures, and this behaviour agrees with previous theoretical studies, thus indicating the inherent difficulties in the theoretical simulation of the kinetics of the title reaction. Different sources of error were analysed, such as the limitations of the PES and theoretical methods, recrossing effects, and the tunnelling effect, which is negligible in this reaction, and the manner in which the spin-orbit effects were included in this non-relativistic study. We found that the variation of spin-orbit coupling along the reaction path, and the influence of the reactivity of the excited Cl( 2 P 1/2 ) state, have relative importance, but do not explain the whole discrepancy. Finally, the

  4. The complex reaction kinetics of neptunium including redox and extraction process in 30% TBP-nitric acid system

    International Nuclear Information System (INIS)

    Hu Zhang; Zhan-yuan Liu; Xian-ming Zhou; Li Li

    2017-01-01

    In order to understand the complex and dynamic neptunium process chemistry in the TBP-HNO_3 system, the kinetics involved reversible redox reaction and extraction mass transfer was investigated. The results indicates that the mass transfer rate of Np(VI) is much faster than the redox reaction in aqueous solution. The concentrations of nitric acid and nitrous acid not only can change the Np(V) oxidation reaction and Np(VI) reduction reaction rate, but also can ultimately determine the distribution of neptunium extraction equilibrium. The variety of temperature can only influence the extraction equilibrium time, but cannot alter the equilibrium state of neptunium. (author)

  5. Principles of chemical kinetics

    CERN Document Server

    House, James E

    2007-01-01

    James House's revised Principles of Chemical Kinetics provides a clear and logical description of chemical kinetics in a manner unlike any other book of its kind. Clearly written with detailed derivations, the text allows students to move rapidly from theoretical concepts of rates of reaction to concrete applications. Unlike other texts, House presents a balanced treatment of kinetic reactions in gas, solution, and solid states. The entire text has been revised and includes many new sections and an additional chapter on applications of kinetics. The topics covered include quantitative rela

  6. An effective rate equation approach to reaction kinetics in small volumes: theory and application to biochemical reactions in nonequilibrium steady-state conditions.

    Science.gov (United States)

    Grima, R

    2010-07-21

    Chemical master equations provide a mathematical description of stochastic reaction kinetics in well-mixed conditions. They are a valid description over length scales that are larger than the reactive mean free path and thus describe kinetics in compartments of mesoscopic and macroscopic dimensions. The trajectories of the stochastic chemical processes described by the master equation can be ensemble-averaged to obtain the average number density of chemical species, i.e., the true concentration, at any spatial scale of interest. For macroscopic volumes, the true concentration is very well approximated by the solution of the corresponding deterministic and macroscopic rate equations, i.e., the macroscopic concentration. However, this equivalence breaks down for mesoscopic volumes. These deviations are particularly significant for open systems and cannot be calculated via the Fokker-Planck or linear-noise approximations of the master equation. We utilize the system-size expansion including terms of the order of Omega(-1/2) to derive a set of differential equations whose solution approximates the true concentration as given by the master equation. These equations are valid in any open or closed chemical reaction network and at both the mesoscopic and macroscopic scales. In the limit of large volumes, the effective mesoscopic rate equations become precisely equal to the conventional macroscopic rate equations. We compare the three formalisms of effective mesoscopic rate equations, conventional rate equations, and chemical master equations by applying them to several biochemical reaction systems (homodimeric and heterodimeric protein-protein interactions, series of sequential enzyme reactions, and positive feedback loops) in nonequilibrium steady-state conditions. In all cases, we find that the effective mesoscopic rate equations can predict very well the true concentration of a chemical species. This provides a useful method by which one can quickly determine the

  7. Effect of ionic strength on the kinetics of ionic and micellar reactions in aqueous solution

    International Nuclear Information System (INIS)

    Dung, M.H.; Kozak, J.J.

    1982-01-01

    The effect of electrostatic forces on the rate of reaction between ions in aqueous solutions of intermediate ionic strength is studied in this paper. We consider the kinetics of reactions involving simple ionic species (1--1 and 2--2 electrolyte systems) as well as kinetic processes mediated by the presence of micellar ions (or other charged organizates). In the regime of ionic strength considered, dielectric saturation of the solvent in the vicinity of the reacting ions must be taken into account and this is done by introducing several models to describe the recovery of the solvent from saturation to its continuum dielectric behavior. To explore the effects of ion size, charge number, and ionic strength on the overall rate constant for the process considered, we couple the traditional theory of ionic reactions in aqueous solution with calculations of the electrostatic potential obtained via solution of the nonlinear Poisson--Boltzmann equation. The great flexibility of the nonlinear Poisson--Boltzmann theory allows us to explore quantitatively the influence of each of these effects, and our simulations show that the short-range properties of the electrostatic potential affect primarily kinetically controlled processes (to varying degrees, depending on the ionic system considered) whereas the down-range properties of the potential play a (somewhat) greater role in influencing diffusion-controlled processes. A detailed examination is made of ionic strength effects over a broad range of ionic concentrations. In the regime of low ionic strength, the limiting slope and intercept of the curve describing the dependence of log k/sub D/ on I/sup 1/2//(1+I/sup 1/2/) may differ considerably from the usual Debye--Hueckel limiting relations, depending on the particular model chosen to describe local saturation effects

  8. 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.

  9. Mineral solubility and free energy controls on microbial reaction kinetics: Application to contaminant transport in the subsurface

    Energy Technology Data Exchange (ETDEWEB)

    Taillefert, Martial [Georgia Inst. of Technology, Atlanta, GA (United States); Van Cappellen, Philippe [Univ. of Waterloo, ON (Canada)

    2016-11-14

    Recent developments in the theoretical treatment of geomicrobial reaction processes have resulted in the formulation of kinetic models that directly link the rates of microbial respiration and growth to the corresponding thermodynamic driving forces. The overall objective of this project was to verify and calibrate these kinetic models for the microbial reduction of uranium(VI) in geochemical conditions that mimic as much as possible field conditions. The approach combined modeling of bacterial processes using new bioenergetic rate laws, laboratory experiments to determine the bioavailability of uranium during uranium bioreduction, evaluation of microbial growth yield under energy-limited conditions using bioreactor experiments, competition experiments between metabolic processes in environmentally relevant conditions, and model applications at the field scale. The new kinetic descriptions of microbial U(VI) and Fe(III) reduction should replace those currently used in reactive transport models that couple catabolic energy generation and growth of microbial populations to the rates of biogeochemical redox processes. The above work was carried out in collaboration between the groups of Taillefert (batch reactor experiments and reaction modeling) at Georgia Tech and Van Cappellen (retentostat experiments and reactive transport modeling) at University of Waterloo (Canada).

  10. Curing behavior and reaction kinetics of binder resins for 3D-printing investigated by dielectric analysis (DEA)

    Science.gov (United States)

    Möginger, B.; Kehret, L.; Hausnerova, B.; Steinhaus, J.

    2016-05-01

    3D-Printing is an efficient method in the field of additive manufacturing. In order to optimize the properties of manufactured parts it is essential to adapt the curing behavior of the resin systems with respect to the requirements. Thus, effects of resin composition, e.g. due to different additives such as thickener and curing agents, on the curing behavior have to be known. As the resin transfers from a liquid to a solid glass the time dependent ion viscosity was measured using DEA with flat IDEX sensors. This allows for a sensitive measurement of resin changes as the ion viscosity changes two to four decades. The investigated resin systems are based on the monomers styrene and HEMA. To account for the effects of copolymerization in the calculation of the reaction kinetics it was assumed that the reaction can be considered as a homo-polymerization having a reaction order n≠1. Then the measured ion viscosity curves are fitted with the solution of the reactions kinetics - the time dependent degree of conversion (DC-function) - for times exceeding the initiation phase representing the primary curing. The measured ion viscosity curves can nicely be fitted with the DC-function and the determined fit parameters distinguish distinctly between the investigated resin compositions.

  11. Field-controlled electron transfer and reaction kinetics of the biological catalytic system of microperoxidase-11 and hydrogen peroxide

    Directory of Open Access Journals (Sweden)

    Yongki Choi

    2011-12-01

    Full Text Available Controlled reaction kinetics of the bio-catalytic system of microperoxidase-11 and hydrogen peroxide has been achieved using an electrostatic technique. The technique allowed independent control of 1 the thermodynamics of the system using electrochemical setup and 2 the quantum mechanical tunneling at the interface between microperoxidase-11 and the working electrode by applying a gating voltage to the electrode. The cathodic currents of electrodes immobilized with microperoxidase-11 showed a dependence on the gating voltage in the presence of hydrogen peroxide, indicating a controllable reduction reaction. The measured kinetic parameters of the bio-catalytic reduction showed nonlinear dependences on the gating voltage as the result of modified interfacial electron tunnel due to the field induced at the microperoxidase-11-electrode interface. Our results indicate that the kinetics of the reduction of hydrogen peroxide can be controlled by a gating voltage and illustrate the operation of a field-effect bio-catalytic transistor, whose current-generating mechanism is the conversion of hydrogen peroxide to water with the current being controlled by the gating voltage.

  12. Atmospheric chemistry of CF3COOH. Kinetics of the reaction with OH radicals

    DEFF Research Database (Denmark)

    Møgelberg, T.E.; Nielsen, O.J.; Sehested, J.

    1994-01-01

    Two different experimental techniques were used to study the kinetics of the reaction of OH radicals with trifluoroacetic acid, CF3COOH. Using a pulse radiolysis absolute rate technique, rate constants at 315 and 348 K were determined to be (1.6 +/- 0.4) x 10(-13) and (1.5 +/- 0.2) x 10(-13) cm3...... molecule-1 s-1, respectively. Using a long path-length FTIR relative rate technique a rate constant of (1.7 +/- 0.5) x 10(-13) cm3 molecule-1 s-1 was obtained at 296 K. In the atmosphere, reaction with OH radicals in the gas phase is estimated to account for 10%-20% of the loss of CF3COOH. The major fate...

  13. Role of Re in Pt-Re/TiO2 catalyst for water gas shift reaction: A mechanistic and kinetic study.

    NARCIS (Netherlands)

    Azzam, K.G.H.; Babych, Igor V.; Seshan, Kulathuiyer; Lefferts, Leonardus

    2008-01-01

    Transient kinetic studies and in situ FTIR spectroscopy were used to follow the reaction sequences that occur during water gas shift (WGS) reaction over Pt–Re/TiO2 catalyst. Results pointed to contributions of an associative formate route with redox regeneration and two classical redox routes

  14. A conceptual model for the fuel oxidation of defective fuel

    International Nuclear Information System (INIS)

    Higgs, J.D.; Lewis, B.J.; Thompson, W.T.; He, Z.

    2007-01-01

    A mechanistic conceptual model has been developed to predict the fuel oxidation behaviour in operating defective fuel elements for water-cooled nuclear reactors. This theoretical work accounts for gas-phase transport and sheath reactions in the fuel-to-sheath gap to determine the local oxygen potential. An improved thermodynamic analysis has also been incorporated into the model to describe the equilibrium state of the oxidized fuel. The fuel oxidation kinetics treatment accounts for multi-phase transport including normal diffusion and thermodiffusion for interstitial oxygen migration in the solid, as well as gas-phase transport in the fuel pellet cracks. The fuel oxidation treatment is further coupled to a heat conduction equation. A numerical solution of the coupled transport equations is obtained by a finite-element technique with the FEMLAB 3.1 software package. The model is able to provide radial-axial profiles of the oxygen-to-uranium ratio and the fuel temperatures as a function of time in the defective element for a wide range of element powers and defect sizes. The model results are assessed against coulometric titration measurements of the oxygen-to-metal profile for pellet samples taken from ten spent defective elements discharged from the National Research Universal Reactor at the Chalk River Laboratories and commercial reactors

  15. Growth kinetics of dislocation loops in irradiated ceramic materials

    International Nuclear Information System (INIS)

    Ryazanov, A.I.; Kinoshita, C.

    2002-01-01

    Ceramic materials are expected to be applied in the future fusion reactor as radio frequency (RF) windows, toroidal insulating breaks and diagnostic probes. The radiation resistance of ceramic materials, degradation of the electrical properties and radiation induced conductivity of these materials under neutron irradiation are determined by the kinetics of the accumulation of point defects in the matrix and point defect cluster formation (dislocation loops, voids, etc.). Under irradiation, due to the ionization process, excitation of electronic subsystem and covalent type of interaction between atoms the point defects in ceramic materials are characterized by the charge state (e.g. an F + center, an oxygen vacancy with a single trapped electron) and the effective charge. For the investigation of radiation resistance of ceramic materials for future fusion applications it is very important to understand the physical mechanisms of formation and growth of dislocation loops and voids under irradiation taking into account in this system the effective charge of point defects. In the present paper the physical mechanisms of dislocation loop growth in ceramic material are investigated. For this aim a theoretical model is suggested for the description of the kinetics of point defect accumulation in the matrix taking into account the charge state of the point defects and the effect of an electric field on diffusion migration process of charged point defects. A self-consistent system of kinetic equations describing the generation of electrical fields near dislocation loops and diffusion migration of charged point defects in elastic and electrical fields is formulated. The solution of the kinetic equations allows to find the growth rate of dislocation loops in ceramic materials under irradiation taking into account the charge state of the point defects and the effect of electric and elastic stress fields near dislocation loop on the diffusion processes

  16. Kinetics, Reaction Orders, Rate Laws, and Their Relation to Mechanisms: A Hands-On Introduction for High School Students Using Portable Spectrophotometry

    Science.gov (United States)

    Carraher, Jack M.; Curry, Sarah M.; Tessonnier, Jean-Philippe

    2016-01-01

    Teaching complex chemistry concepts such as kinetics using inquiry-based learning techniques can be challenging in a high school classroom setting. Access to expensive laboratory equipment such as spectrometers is typically limited and most reaction kinetics experiments have been designed for advanced placement (AP) or first-year undergraduate…

  17. Non-equilibrium reactive flux: A unified framework for slow and fast reaction kinetics.

    Science.gov (United States)

    Bose, Amartya; Makri, Nancy

    2017-10-21

    The flux formulation of reaction rate theory is recast in terms of the expectation value of the reactive flux with an initial condition that corresponds to a non-equilibrium, factorized reactant density. In the common case of slow reactive processes, the non-equilibrium expression reaches the plateau regime only slightly slower than the equilibrium flux form. When the reactants are described by a single quantum state, as in the case of electron transfer reactions, the factorized reactant density describes the true initial condition of the reactive process. In such cases, the time integral of the non-equilibrium flux expression yields the reactant population as a function of time, allowing characterization of the dynamics in cases where there is no clear separation of time scales and thus a plateau regime cannot be identified. The non-equilibrium flux offers a unified approach to the kinetics of slow and fast chemical reactions and is ideally suited to mixed quantum-classical methods.

  18. The kinetics of free radical metathetical and addition reactions in silane solutions

    International Nuclear Information System (INIS)

    Aloni, R.

    1976-12-01

    In this work radiolytic technique was employed for the initiation of free radical chainreactions in silane solution. The kinetic analysis of the chain mechanism in various solutions enabled the determination of the Arrhenius parameters for metathesis, addition and unimolecular decomposition reactions which make up the chainpropagation sequence in the systems studied. The following radical reactions were investigated: chlorine atom abstraction from chloromethanes by SiCl 3 and Et 3 Si radicals, and chlorine atom abstraction from chloroethanes by Et 3 Si radicals; unimolecular decomposition reactions and hydrogen atom abstraction, *from the solvent, of chloroethyl radicals in triethylsilane solutions; addition and abstraction reactions of Et 3 Si radicals with chloroolefins. Arrhenius parameters were determined for abstraction of chlorine atom from CH 3 Cl, CH 2 Cl 2 , CHCl 3 and CCl 4 , by SiCl 3 radicals and from CCl 4 , CHCl 3 , CH 2 Cl 2 , CCl 3 CN, C 2 Cl 5 H, sym-C 2 Cl 4 H 2 , asym-C 2 Cl 4 H 2 , 1.1.1-C 2 Cl 3 H 3 , 1.1.1-C 2 Dl 3 F 3 and 1.1-C 2 Cl 2 H 4 by Et 3 Si radicals. (author)

  19. Defect-induced Catalysis toward the Oxygen Reduction Reaction in Single-walled Carbon Nanotube: Nitrogen doped and Non-nitrogen doped

    International Nuclear Information System (INIS)

    Lu, Di; Wu, Dan; Jin, Jian; Chen, Liwei

    2016-01-01

    Single-walled carbon nanotubes (SWNTs) are post-treated by argon (Ar) or ammonia (NH 3 ) plasma irradiation to introduce defects that are potentially related to catalysis towards the oxygen reduction reaction (ORR). Electrochemical characterization in alkali medium suggests that the plasma irradiated SWNTs demonstrate enhanced catalytic activity toward the ORR with a positively shifted threshold potential. Moreover the enhanced desired four-electron pathway catalytic activity, which exhibited as the positive shifted threshold potential, is independent of the nitrogen dopant. The nature of the defects is probed with Raman and X-ray photoelectron spectroscopy. The results indicate that the non-nitrogen doped defects of SWNTs contribute to the actual active site for the ORR.

  20. The relationship between reaction kinetics and mutagenic action of monofunctional alkylating agents in higher eukaryotic systems. IV. The effects of the excision-defective mei-9L1 and mus(2)201D1 mutants on alkylation-induced genetic damage in Drosophila.

    Science.gov (United States)

    Vogel, E W; Dusenbery, R L; Smith, P D

    1985-04-01

    Repair-defective mutants of Drosophila melanogaster which identify two major DNA excision repair loci have been examined for their effects on alkylation-induced mutagenesis using the sex-linked recessive lethal assay as a measure of genotoxic endpoint. The alkylating agents (AAs) chosen for comparative analysis were selected on the basis of their reaction kinetics with DNA and included MMS, EMS, MNU, DMN, ENU, DEN and ENNG. Repair-proficient males were treated with the AAs and mated with either excision-defective mei-9L1 or mus(2)201D1 females or appropriate excision-proficient control females. The results of the present work suggest that a qualitative and quantitative relationship exists between the nature and the extent of chemical modification of DNA and the induction of of genetic alterations. The presence of either excision-defective mutant can enhance the frequency of mutation (hypermutability) and this hypermutability can be correlated with the Swain-Scott constant S of specific AAs such that as the SN1 character of the DNA alkylation reaction increases, the difference in response between repair-deficient and repair-proficient females decreases. The order of hypermutability of AAs with mei-9L1 relative to mei-9+ is MMS greater than MNU greater than DMN = EMS greater than iPMS = ENU = DEN = ENNG. When the percentage of lethal mutations induced in mei-9L1 females are plotted against those determined for control females, straight lines of different slopes are obtained. These mei-9L1/mei-9+ indices are: MMS = 7.6, MNU = 5.4, DMN = 2.4, EMS = 2.4 and iPMS = ENU = DEN = ENNG = 1. An identical order of hypermutability with similar indices is obtained for the mus(2)201 mutants: MMS(7.3) greater than MNU (5.4) greater than EMS(2.0) greater than ENU(1.1). Thus, absence of excision repair function has a significant effect on mutation production by AAs efficient in alkylating N-atoms in DNA but no measurable influence on mutation production by AAs most efficient in

  1. Secondary hydriding of defected zircaloy-clad fuel rods

    International Nuclear Information System (INIS)

    Olander, D.R.; Vaknin, S.

    1993-01-01

    The phenomenon of secondary hydriding in LWR fuel rods is critically reviewed. The current understanding of the process is summarized with emphasis on the sources of hydrogen in the rod provided by chemical reaction of water (steam) introduced via a primary defect in the cladding. As often noted in the literature, the role of hydrogen peroxide produced by steam radiolysis is to provide sources of hydrogen by cladding and fuel oxidation that are absent without fission-fragment irradiation of the gas. Quantitative description of the evolution of the chemical state inside the fuel rod is achieved by combining the chemical kinetics of the reactions between the gas and the fuel and cladding with the transport by diffusion of components of the gas in the gap. The chemistry-gas transport model provides the framework into which therate constants of the reactions between the gases in the gap and the fuel and cladding are incorporated. The output of the model calculation is the H 2 0/H 2 ratio in the gas and the degree of claddingand fuel oxidation as functions of distance from the primary defect. This output, when combined with a criterion for the onset of massive hydriding of the cladding, can provide a prediction of the time and location of a potential secondary hydriding failure. The chemistry-gas transport model is the starting point for mechanical and H-in-Zr migration analyses intended to determine the nature of the cladding failure caused by the development of the massive hydride on the inner wall

  2. Kinetics and thermochemistry of the reversible gas phase reaction HONO+NH3->3N-HONO studied by infrared diode laser spectroscopy

    DEFF Research Database (Denmark)

    Pagsberg, P.; Ratajczak, E.; Sillesen, A.

    1994-01-01

    The kinetics of the reversible reaction HONO+NH3 reversible H3N-HONO (1) was studied by monitoring trans-HONO relaxation kinetics. The rate of approach towards equilibrium was studied as a function of the ammonia concentration to obtain values of the rate constants for the forward and reverse rea...

  3. Kinetics and mechanism of oxygen reduction reaction at CoPd system synthesized on XC72

    International Nuclear Information System (INIS)

    Tarasevich, M.R.; Chalykh, A.E.; Bogdanovskaya, V.A.; Kuznetsova, L.N.; Kapustina, N.A.; Efremov, B.N.; Ehrenburg, M.R.; Reznikova, L.A.

    2006-01-01

    Studies are presented of the kinetics and mechanism of oxygen electroreduction reaction on CoPd catalysts synthesized on carbon black XC72. As shown both in model conditions and in the tests within the cathodes of hydrogen-oxygen fuel cells with proton conducting electrolyte, CoPd/C system features a higher activity, as compared to Co/C. The highest activity in the oxygen reduction reaction is demonstrated by the catalysts with the Pd:Co atomic ratio being 7:3 and 4:1. The structural studies (XPS and XRD, and also the data of CO desorption measurements) evidence the CoPd alloy formation, which is reflected in the negative shift of the bonding energy maximum as compared to Pd/C and in the appearance of the additional CO desorption maximums on the voltammograms. It is found by means of structural research that CoPd alloy is formed in the course of the catalyst synthesis which features a higher catalytic activity of the binary systems. Besides, CoPd/C catalyst is more stable in respect to corrosion than Pd supported on carbon black. The measurements on the rotating disc electrode and rotating ring-disc electrode evidence that CoPd/C system provides the predominant oxygen reduction to water in the practically important range of potentials (E > 0.7 V). The proximity of kinetic parameters of the oxygen reduction reaction on CoPd/C and Pt/C catalysts points to the similar reaction mechanism. The slow step of the reaction is the addition of the first electron to the adsorbed and previously protonated O 2 molecule. The assumptions are offered about the reasons causing the higher activity and selectivity of the binary catalyst towards oxygen reduction to water, as compared to Co/C. The studies of the most active catalysts within the fuel cell cathodes are performed

  4. Reaction kinetics and transformation of carbadox and structurally related compounds with aqueous chlorine.

    Science.gov (United States)

    Shah, Amisha D; Kim, Jae-Hong; Huang, Ching-Hua

    2006-12-01

    The potential release of carbadox (CDX), a commonly used antibacterial agent in swine husbandry, into water systems is of a concern due to its carcinogenic and genotoxic effects. Until this study, the reactivity of carbadox (possessing quinoxaline N,N'-dioxide and hydrazone moieties) toward aqueous chlorine has yetto be investigated in depth. Chemical reactivity, reaction kinetics, and transformation pathways of carbadox and structurally related compounds with free chlorine under typical water treatment conditions were determined. This study found that only CDX and desoxycarbadox (DCDX), a main metabolite of CDX with no ring N-oxide groups, react rapidly with free chlorine while other structurally related compounds including olaquindox, quindoxin, quinoxaline N-oxide, quinoxaline, and quinoline N-oxide do not. The reaction kinetics of CDX and DCDX with chlorine are highly pH dependent (e.g., the apparent second-order rate constant, kapp, for CDX ranges from 51.8 to 3.15 x 10(4) M(-1)s(-1) at pH 4-11). The high reactivity of CDX and DCDX to chlorine involves deprotonation of their hydrazone N-H moieties where initial chlorine attack results in a reactive intermediate that is further attacked by nucleophiles in the matrix to yield non-chlorinated, hydroxylated, and larger molecular weight byproducts. All of the CDX's byproducts retain their biologically active N-oxide groups, suggesting that they may remain as active antibacterial agents.

  5. Nonmonotonic Temperature Dependence of the Pressure-Dependent Reaction Rate Constant and Kinetic Isotope Effect of Hydrogen Radical Reaction with Benzene Calculated by Variational Transition-State Theory.

    Science.gov (United States)

    Zhang, Hui; Zhang, Xin; Truhlar, Donald G; Xu, Xuefei

    2017-11-30

    The reaction between H and benzene is a prototype for reactions of radicals with aromatic hydrocarbons. Here we report calculations of the reaction rate constants and the branching ratios of the two channels of the reaction (H addition and H abstraction) over a wide temperature and pressure range. Our calculations, obtained with an accurate potential energy surface, are based on variational transition-state theory for the high-pressure limit of the addition reaction and for the abstraction reaction and on system-specific quantum Rice-Ramsperger-Kassel theory calibrated by variational transition-state theory for pressure effects on the addition reaction. The latter is a very convenient way to include variational effects, corner-cutting tunneling, and anharmonicity in falloff calculations. Our results are in very good agreement with the limited experimental data and show the importance of including pressure effects in the temperature interval where the mechanism changes from addition to abstraction. We found a negative temperature effect of the total reaction rate constants at 1 atm pressure in the temperature region where experimental data are missing and accurate theoretical data were previously missing as well. We also calculated the H + C 6 H 6 /C 6 D 6 and D + C 6 H 6 /C 6 D 6 kinetic isotope effects, and we compared our H + C 6 H 6 results to previous theoretical data for H + toluene. We report a very novel nonmonotonic dependence of the kinetic isotope effect on temperature. A particularly striking effect is the prediction of a negative temperature dependence of the total rate constant over 300-500 K wide temperature ranges, depending on the pressure but generally in the range from 600 to 1700 K, which includes the temperature range of ignition in gasoline engines, which is important because aromatics are important components of common fuels.

  6. Study by nuclear techniques of the impurity-defect interaction in implanted metals

    International Nuclear Information System (INIS)

    Thome, Lionel.

    1978-01-01

    The properties of out equilibrium alloys formed by impurity implantation are strongly influenced by radiation damage created during implantation. This work presents a study, via hyperfine interaction and lattice location experiments, of the impurity-defect interaction in ion implanted metals. When the impurity and defect concentrations in the implanted layer are small, i.e. when impurities are uniformly recoil implanted in the whole crystal volume following a nuclear reaction (Aq In experiments), the impurity interacts with its own damage cascade. In this case, a vacancy is found to be trapped by a fraction of impurities during an athermal process. The value of this fraction does not seem to depend critically on impurity and host. When the impurity and defect concentrations are such that defect cascades interact, i.e. when impurities are implanted with an isotope separator (Fe Yb experiments), the observed impurity-vacancy (or vacancy cluster) interactions depend then strongly on the nature of impurity and host. An empirical relation, which indicates the importance of elastic effects, has been found between the proportion of impurities interacting with defects and the difference between impurity and host atom radii. At implantation temperature such that vacancies are mobile, the impurity-defect interaction depends essentially on vacancy migration. A model based on chemical kinetics has been developed to account for the variation with temperature of measured quantities [fr

  7. Catecholase activity of dicopper(II)-bispidine complexes: stabilities and structures of intermediates, kinetics and reaction mechanism.

    Science.gov (United States)

    Born, Karin; Comba, Peter; Daubinet, André; Fuchs, Alexander; Wadepohl, Hubert

    2007-01-01

    A mechanism for the oxidation of 3,5-di-tert-butylcatechol (dtbc) with dioxygen to the corresponding quinone (dtbq), catalyzed by bispidine-dicopper complexes (bispidines are various mono- and dinucleating derivatives of 3,7-diazabicyclo[3.3.1]nonane with bis-tertiary-amine-bispyridyl or bis-tertiary-amine-trispyridyl donor sets), is proposed on the basis of (1) the stoichiometry of the reaction as well as the stabilities and structures [X-ray, density functional theory (B3LYP, TZV)] of the bispidine-dicopper(II)-3,4,5,6-tetrachlorcatechol intermediates, (2) formation kinetics and structures (molecular mechanics, MOMEC) of the end-on peroxo-dicopper(II) complexes and (3) kinetics of the stoichiometric (anaerobic) and catalytic (aerobic) copper-complex-assisted oxidation of dtbc. This involves (1) the oxidation of the dicopper(I) complexes with dioxygen to the corresponding end-on peroxo-dicopper(II) complexes, (2) coordination of dtbc as a bridging ligand upon liberation of H(2)O(2) and (3) intramolecular electron transfer to produce dtbq, which is liberated, and the dicopper(I) catalyst. Although the bispidine complexes have reactivities comparable to those of recently published catalysts with macrocyclic ligands, which seem to reproduce the enzyme-catalyzed process in various reaction sequences, a strikingly different oxidation mechanism is derived from the bispidine-dicopper-catalyzed reaction.

  8. In situ synchrotron powder diffraction study of the setting reaction kinetics of magnesium-potassium phosphate cements

    Czech Academy of Sciences Publication Activity Database

    Viani, Alberto; Pérez-Estébanez, Marta; Pollastri, S.; Gualtieri, A. F.

    2016-01-01

    Roč. 79, January (2016), s. 344-352 ISSN 0008-8846 R&D Projects: GA MŠk(CZ) LO1219 Keywords : kinetics * reaction * X-ray diffraction * MgO * chemically bonded ceramics Subject RIV: JN - Civil Engineering Impact factor: 4.762, year: 2016 http://www.sciencedirect.com/science/article/pii/S0008884615002690

  9. Kinetics and mechanistic study of n-alkane hydroisomerization reaction on Pt-doped γ-alumina catalyst

    Directory of Open Access Journals (Sweden)

    Abhishek Dhar

    2017-12-01

    Full Text Available The catalysts γ-alumina (GA, the reference catalyst and Pt doped γ-alumina (PGA-s were synthesized using a simple sol-gel technique, in which at first preparation of porous base (GA, then impregnation of platinum salt over the base and finally reduction of platinum in the surface of the support were done. These catalysts prepared in different mole ratios of Pt:Al as 2:1, 1:1 and 1:2 are named as PGA-1, PGA-2 and PGA-3 respectively. The isomerization of n-alkanes (n-hexane, n-heptane and n-octane were investigated over the synthesized catalysts. The 2-methyl pentane (2-MP, 2,2-dimethyl pentane (2,2-DMP and 2,3-dimethyl hexane (2,3-DMH are the major products of respective isomerization of n-hexane, n-heptane and n-octane, besides a small amount of other branched isomers are also produced. The product distribution is comparable to that reported for Pt based other catalysts. The optimal mole ratios of Pt:Al is 1:1 (PGA-2 gives quite good catalytic activity for isomerization of n-alkane. Even through in reusability study, PGA-2 gives better performance than others. We have mainly focused on kinetic study, reaction mechanism behind isomerization and calculated the order of reactions and activation energies of the isomerization reactions in the present work. Keywords: Isomerization, n-alkanes, Catalyst, Reaction mechanism, Kinetics study, Activation energy

  10. A-centres build-up kinetics in the conductive matrix of pulled n-type silicon with calculation of their recharges at defect clusters

    International Nuclear Information System (INIS)

    Dolgolenko, A.P.; Fishchuk, I.I.

    1981-01-01

    Pulled n-Si samples with rho approximately 40 Ωcm are investigated after irradiation with different doses of fast-pile neutrons. It is known that the simple defects are created not only in the conductive matrix but also in the region of the space charge of defect clusters. Then the charge state, for example, of A-centres in the region of the space charge is defined by both, the temperature and the value of the electrostatical potential. If this circumstance is not taken into account the calculation of the conductive volume is not precise enough. In the present paper the temperature dependence of the volume fraction is calculated, in which the space charge of defect clusters occurs, taking into account the recharges of A-centres in the region of the space charge. Using the expression obtained the A-centres build-up kinetics in the conductive matrix of pulled n-type silicon is calculated. (author)

  11. Kinetics of the reaction of F atoms with O2 and UV spectrum of FO2 radicals in the gas phase at 295 K

    DEFF Research Database (Denmark)

    Ellermann, T.; Sehested, J.; Nielsen, O.J.

    1994-01-01

    The ultraviolet absorption spectrum of FO2 radicals and the kinetics of the reaction of F atoms with O2 have been studied in the gas phase at 295 K using pulse radiolysis combined with kinetic UV spectroscopy. At 230 nm, sigma(FO2) = (5.08 +/- 0.70) X 10(-18) cm2 molecule-1. The kinetics of the r......The ultraviolet absorption spectrum of FO2 radicals and the kinetics of the reaction of F atoms with O2 have been studied in the gas phase at 295 K using pulse radiolysis combined with kinetic UV spectroscopy. At 230 nm, sigma(FO2) = (5.08 +/- 0.70) X 10(-18) cm2 molecule-1. The kinetics...

  12. Importance of (n,xn) reactions in evaluating kinetic parameters of subcritical assemblies: from classic to modern formalism

    Energy Technology Data Exchange (ETDEWEB)

    Talamo, Alberto; Gohar, Yousry, E-mail: alby@anl.gov [Argonne National Laboratory, Lemont, IL (United States); Dulla, Sandra; Ravetto, Piero [Politecnico di Torino (Italy)

    2011-07-01

    The importance of (n,xn) reactions must be taken into consideration while calculating the kinetic parameters of subcritical assemblies driven by an external neutron source. This study is divided into two parts, the first part is dedicated to the classic definition of the neutron source multiplication factor and two alternative calculation methodologies are compared. The second part considers a new definition of the kinetic parameters for subcritical assemblies, with particular emphasis on the delayed neutron fraction and generation time. This new definition has been modified to take into account the external neutron source and (n,xn) reactions, which increase the fraction of prompt neutrons. The developed theoretical framework has been applied by Monte Carlo and deterministic calculations to the YALINA Thermal subcritical assembly in Belarus. This facility can be driven by californium, deuterium-deuterium (D-D), or deuterium-tritium (D-T) external neutron sources. For the D-T neutron source, (n,xn) reactions must be taken into account in order to produce accurate results because the average energy of D-T source neutrons is 14.1 MeV, a value much higher than the threshold energy of the (n,2n) cross section of uranium isotopes. (author)

  13. Importance of (n,xn) reactions in evaluating kinetic parameters of subcritical assemblies: from classic to modern formalism

    International Nuclear Information System (INIS)

    Talamo, Alberto; Gohar, Yousry; Dulla, Sandra; Ravetto, Piero

    2011-01-01

    The importance of (n,xn) reactions must be taken into consideration while calculating the kinetic parameters of subcritical assemblies driven by an external neutron source. This study is divided into two parts, the first part is dedicated to the classic definition of the neutron source multiplication factor and two alternative calculation methodologies are compared. The second part considers a new definition of the kinetic parameters for subcritical assemblies, with particular emphasis on the delayed neutron fraction and generation time. This new definition has been modified to take into account the external neutron source and (n,xn) reactions, which increase the fraction of prompt neutrons. The developed theoretical framework has been applied by Monte Carlo and deterministic calculations to the YALINA Thermal subcritical assembly in Belarus. This facility can be driven by californium, deuterium-deuterium (D-D), or deuterium-tritium (D-T) external neutron sources. For the D-T neutron source, (n,xn) reactions must be taken into account in order to produce accurate results because the average energy of D-T source neutrons is 14.1 MeV, a value much higher than the threshold energy of the (n,2n) cross section of uranium isotopes. (author)

  14. A Mathematical Model for the Multiphase Transport and Reaction Kinetics in a Ladle with Bottom Powder Injection

    Science.gov (United States)

    Lou, Wentao; Zhu, Miaoyong

    2017-12-01

    A computation fluid dynamics-population balance model-simultaneous reaction model (CFD-PBM-SRM) coupled model has been proposed to study the multiphase flow behavior and refining reaction kinetics in a ladle with bottom powder injection, and some new and important phenomena and mechanisms are presented. For the multiphase flow behavior, the effects of bubbly plume flow, powder particle motion, particle-particle collision and growth, particle-bubble collision and adhesion, and powder particle removal into top slag are considered. For the reaction kinetics, the mechanisms of multicomponent simultaneous reactions, including Al, S, Si, Mn, Fe, and O, at the multi-interface, including top slag-liquid steel interface, air-liquid steel interface, powder droplet-liquid steel interface, and bubble-liquid steel interface, are presented, and the effect of sulfur solubility in the powder droplet on the desulfurization is also taken into account. Model validation is carried out using hot tests in a 2-t induction furnace with bottom powder injection. The result shows that the powder particles gradually disperse in the entire furnace; in the vicinity of the bottom slot plugs, the desulfurization product CaS is liquid phase, while in the upper region of the furnace, the desulfurization product CaS is solid phase. The predicted sulfur contents by the present model agree well with the measured data in the 2-t furnace with bottom powder injection.

  15. On kinetics of paramagnetic radiation defects accumulation in beryllium ceramics

    International Nuclear Information System (INIS)

    Polyakov, A.I.; Ryabikin, Yu.A.; Zashkvara, O.V.; Bitenbaev, M.I.; Petykhov, Yu.V.

    1999-01-01

    Results of paramagnetic radiation defects concentration dependence study in beryllium ceramics from gamma-irradiation dose ( 60 Co) within interval 0-100 Mrem are cited. Obtained dose dependence has form of accumulation curve with saturation typical of for majority of solids (crystals, different polymers, organic substances and others) , in which under irradiation occur not only formation of paramagnetic radiation defects, but its destruction due to recombination and interaction with radiation fields. Analysis of accumulation curve by the method of distant asymptotics allows to determine that observed in gamma-irradiated beryllium ceramics double line of electron spin resonance is forming of two types of paramagnetic radiation defects. It was defined, that sum paramagnetic characteristics of beryllium ceramics within 1-100 Mrad gamma- irradiation dose field change insignificantly and define from first type of paramagnetic radiation defects

  16. Classical Example of Total Kinetic and Thermodynamic Control: The Diels-Alder Reaction between DMAD and Bis-furyl Dienes.

    Science.gov (United States)

    Borisova, Kseniya K; Kvyatkovskaya, Elizaveta A; Nikitina, Eugeniya V; Aysin, Rinat R; Novikov, Roman A; Zubkov, Fedor I

    2018-04-20

    A rare example of chemospecificity in the tandem Diels-Alder reaction of activated alkynes and bis-dienes has been revealed. The reaction between bis-furyl dienes and DMAD occurs at 25-80 °C and leads to kinetically controlled "pincer" adducts, 4a,8a-disubstituted 1,4:5,8-diepoxynaphthalenes. On the contrary, only thermodynamically controlled "domino" adducts (2,3-disubstituted 1,4:5,8-diepoxynaphthalenes) are formed in the same reaction at 140 °C. The "pincer" adducts can be transformed to the "domino" adducts at heating. The rate constants for reactions of both types were calculated using dynamic 1 H NMR spectroscopy.

  17. Interplay between excitation kinetics and reaction-center dynamics in purple bacteria

    International Nuclear Information System (INIS)

    Caycedo-Soler, Felipe; RodrIguez, Ferney J; Quiroga, Luis; Johnson, Neil F

    2010-01-01

    Photosynthesis is arguably the fundamental process of life, since it enables energy from the Sun to enter the food chain on the Earth. It is a remarkable non-equilibrium process in which photons are converted to many-body excitations, which traverse a complex biomolecular membrane, where they are captured and fuel chemical reactions within a reaction center (RC) in order to produce nutrients. The precise nature of these dynamical processes-which lie at the interface between quantum and classical behavior and involve both noise and coordination-is still being explored. Here, we focus on a striking recent empirical finding concerning an illumination-driven transition in the biomolecular membrane architecture of the purple bacteria Rsp. photometricum. Using stochastic realizations to describe a hopping rate model for excitation transfer, we show numerically and analytically that this surprising shift in preferred architectures can be traced to the interplay between the excitation kinetics and the RC dynamics. The net effect is that the bacteria profit from efficient metabolism at low illumination intensities while using dissipation to avoid an oversupply of energy at high illumination intensities.

  18. Prediction and validation of burnout curves for Goettelborn char using reaction kinetics determined in shock tube experiments

    Energy Technology Data Exchange (ETDEWEB)

    Moors, J.H.J.; Banin, V.E.; Haas, J.H.P.; Weber, R.; Veefkind, A. [Eindhoven University of Technology, Eindhoven (Netherlands). Dept. of Applied Physics

    1999-01-01

    Using a shock tube facility the combustion characteristics of pulverised char ({lt} 10 {mu}m) were measured. A prediction was made for the burnout behaviour of a commercial sized char particle (75-90 {mu}m) in different ambient conditions using a `pseudo kinetic` approach. In this approach the kinetic rate of a surface containing micro pores is determined and these `pseudo kinetics` are then applied to the larger particle not taking into account the micro pores. Comparison of the predictions with measurements done with an isothermal plug flow reactor showed this approach to be valid within experimental error for low burnout. A linear decrease of the kinetic reaction rate with burnout is shown to predict the burnout behaviour in the complete range of burnout. A possible explanation for this linear decrease could be a growing fraction of non-combustible material in the char particles during burnout. 11 refs., 6 figs., 2 tabs.

  19. Investigation of the kinetic mechanism of the demanganization reaction between carbon-saturated liquid iron and CaF2-CaO-SiO2-based slags

    Science.gov (United States)

    Duan, Sheng-chao; Li, Chuang; Guo, Han-jie; Guo, Jing; Han, Shao-wei; Yang, Wen-sheng

    2018-04-01

    The demanganization reaction kinetics of carbon-saturated liquid iron with an eight-component slag consisting of CaO-SiO2-MgO-FeO-MnO-Al2O3-TiO2-CaF2 was investigated at 1553, 1623, and 1673 K in this study. The rate-controlling step (RCS) for the demanganization reaction with regard to the hot metal pretreatment conditions was studied via kinetics analysis based on the fundamental equation of heterogeneous reaction kinetics. From the temperature dependence of the mass transfer coefficient of a transition-metal oxide (MnO), the apparent activation energy of the demanganization reaction was estimated to be 189.46 kJ·mol-1 in the current study, which indicated that the mass transfer of MnO in the molten slag controlled the overall rate of the demanganization reaction. The calculated apparent activation energy was slightly lower than the values reported in the literature for mass transfer in a slag phase. This difference was attributed to an increase in the "specific reaction interface" (SRI) value, either as a result of turbulence at the reaction interface or a decrease of the absolute amount of slag phase during sampling, and to the addition of calcium fluoride to the slag.

  20. Kinetics of the reaction between H· and superheated water probed with muonium

    International Nuclear Information System (INIS)

    Alcorn, Chris D.; Brodovitch, Jean-Claude; Percival, Paul W.; Smith, Marisa; Ghandi, Khashayar

    2014-01-01

    Highlights: • Rate constants for reactions of H with water resolve a controversy. • H reacts with superheated water via two channels. • The findings have important implications for the safety of some nuclear power reactors. - Abstract: Safe operation of supercritical water-cooled reactors requires knowledge of the kinetics of transient species formed by the radiolysis of water in the range 300–650 °C. Using muonium, it is possible to study aqueous H · atom chemistry over this temperature range. An important reaction to study is that of the H · atom with water itself, because it is a potential source of molecular H 2 . The concentration of H 2 is important to plant coolant chemistry, as H 2 is currently added to suppress oxidative corrosion in CANDU reactors. The reaction of muonium with H 2 O and D 2 O was studied experimentally up to 450 °C, and also via quantum chemical computations to investigate possible isotope effects. Our results suggest that although the H · atom abstraction from H 2 O is important at temperatures above 300 °C, the electron-producing channel (H · + H 2 O ⇌ H 3 O + + e aq - ) is significant at temperatures up to 300 °C, and becomes the dominant reaction channel at lower temperatures

  1. 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.

  2. The binding of quinone to the photosynthetic reaction centers: kinetics and thermodynamics of reactions occurring at the QB-site in zwitterionic and anionic liposomes.

    Science.gov (United States)

    Mavelli, Fabio; Trotta, Massimo; Ciriaco, Fulvio; Agostiano, Angela; Giotta, Livia; Italiano, Francesca; Milano, Francesco

    2014-07-01

    Liposomes represent a versatile biomimetic environment for studying the interaction between integral membrane proteins and hydrophobic ligands. In this paper, the quinone binding to the QB-site of the photosynthetic reaction centers (RC) from Rhodobacter sphaeroides has been investigated in liposomes prepared with either the zwitterionic phosphatidylcholine (PC) or the negatively charged phosphatidylglycerol (PG) to highlight the role of the different phospholipid polar heads. Quinone binding (K Q) and interquinone electron transfer (L AB) equilibrium constants in the two type of liposomes were obtained by charge recombination reaction of QB-depleted RC in the presence of increasing amounts of ubiquinone-10 over the temperature interval 6-35 °C. The kinetic of the charge recombination reactions has been fitted by numerically solving the ordinary differential equations set associated with a detailed kinetic scheme involving electron transfer reactions coupled with quinone release and uptake. The entire set of traces at each temperature was accurately fitted using the sole quinone release constants (both in a neutral and a charge separated state) as adjustable parameters. The temperature dependence of the quinone exchange rate at the QB-site was, hence, obtained. It was found that the quinone exchange regime was always fast for PC while it switched from slow to fast in PG as the temperature rose above 20 °C. A new method was introduced in this paper for the evaluation of constant K Q using the area underneath the charge recombination traces as the indicator of the amount of quinone bound to the QB-site.

  3. Elucidation of reaction mechanism for m -cresol hydrodeoxygenation over Fe based catalysts: A kinetic study

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Yongchun; Wang, Yong

    2017-09-01

    Fe based catalysts are promising for hydrodeoxygenation (HDO) of lignin derived phenolics due to their high selectivity for aromatics. In this work, the reaction mechanism of m-cresol HDO on Fe catalysts and the kinetic consequence with Pd addition were elucidated by examining the effect of H2, H2O and m-cresol pressures on toluene formation rate on Fe and PdFe catalysts. A direct CO bond cleavage mechanism is proposed for HDO catalysis on both Fe and PdFe catalysts, while Pd provides a facilitated reaction pathway at the PdFe interface and therefore promotes the catalysis on Fe without changing the high selectivity towards aromatics.

  4. Kinetics of the rapid reaction Br/sub 2/ + 2 I/sup -/. -->. I/sub 2/ + 2 Br/sup -/ in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Rao, T S; Mali, S I; Dangat, V T [Presidency Coll., Calcutta (India). Dept. of Chemistry

    1979-01-01

    The displacement of iodine from aqueous iodide ion solutions by bromine is a rapid reaction whose kinetics has been studied by the competition technique. The reaction is of second order, having a specific rate of 6.85 x 10/sup 5/ M/sup -1/ s/sup -1/ at 25.0 /sup 0/C and energy of activation of 30.8 kJ mol/sup -1/. A mechanism for the reaction is proposed.

  5. Intrinsic reaction kinetics of coal char combustion by direct measurement of ignition temperature

    International Nuclear Information System (INIS)

    Kim, Ryang-Gyoon; Jeon, Chung-Hwan

    2014-01-01

    A wire heating reactor that can use a synchronized experimental method was developed to obtain the intrinsic kinetics of large coal char particles ranging in size from 0.4 to 1 mm. This synchronization system consists of three parts: a thermocouple wire for both heating and direct measurement of the particle temperature, a photodetector sensor for determining ignition/burnout points by measuring the intensity of luminous emission from burning particles, and a high-speed camera–long-distance microscope for observing and recording the movement of luminous zone directly. Coal char ignition was found to begin at a spot on the particle's external surface and then moved across the entire particle. Moreover, the ignition point determined according to the minimum of dT/dt is a spot point and not a full growth point. The ignition temperature of the spot point rises as the particle diameter increases. A spot ignition model, which describes the ignition in terms of the internal conduction and external/internal oxygen diffusion, was then developed to evaluate the intrinsic kinetics and predict the ignition temperature of the coal char. Internal conduction was found to be important in large coal char particles because its effect becomes greater than that of oxygen diffusion as the particle diameter increases. In addition, the intrinsic kinetics of coal char obtained from the spot ignition model for two types of coal does not differ significantly from the results of previous investigators. -- Highlights: • A novel technique was used to measure the coal char particle temperature. • The ignition point determined from a dT/dt minimum is a spot ignition point. • A spot ignition model was suggested to analyze the intrinsic reaction kinetics of coal char. • Internal conduction has to be considered in order to evaluate the intrinsic kinetics for larger particle (above 1 mm)

  6. Kinetic Modeling of the Reaction Rate for Quartz and Carbon Black Pellet

    Science.gov (United States)

    Li, Fei; Tangstad, Merete

    2018-06-01

    The kinetic modeling for the carbothermal reduction reaction rate in quartz and carbon black pellets is studied at different temperatures, under varying CO partial pressures in ambient atmosphere, varying carbon contents, different quartz particle sizes, and different crucible opening areas. Carbon black is produced by the cracking of natural gas. The activation energy of the SiC-producing step was determined to be 594 kJ/mol. The averaged pre-exponential factor A obtained from 1898 K, 1923 K, and 1948 K (1625 °C, 1650 °C, and 1675 °C) is 2.62E+16 min-1. The reaction rate of the gas-solid interface factor, fix-C content ( X fix-C), temperature ( T), and CO partial pressure ( X CO) can be expressed as follows: {{d/pct}}{{{d}t}} = (1 - 0.40 × X_{{{fix} - C}}^{ - 0.86} × {pct}) × 2.62 × 10^{16} × \\exp ( { - 594000/RT} ) × (2.6 - 0.015 × X_{co} ).

  7. Kinetic modeling of hydrocracking reaction in a trickle-bed reactor with Pt/Y-zeolite catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Lee, BalSang; Park, Myung-June; Kim, Young-A; Park, Eun Duck [Ajou University, Suwon (Korea, Republic of); Han, Jeongsik [Agency for Defense Development, Daejeon (Korea, Republic of); Jeong, Kwang-Eun; Kim, Chul-Ung; Jeong, Soon-Yong [Korea Research Institute of Chemical Technology (KRICT), Daejeon (Korea, Republic of)

    2014-03-15

    A kinetic model is developed to predict the entire distribution of hydrocarbon products for the hydrocracking reaction with Pt/Y-zeolite catalysts in a trickle-bed reactor. Operating conditions, such as temperature, pressure, and wax and H{sub 2} flow rates were varied to evaluate their effects on conversion and distribution, and kinetic parameters were estimated using the experimental data that covers the window of operating conditions. The comparison between experimental data and simulated results corroborated the validity of the developed model, and the quantitative prediction of the reactor performance was clearly demonstrated. To make evident the usefulness of the model, an optimization method, genetic algorithm (GA), was applied, and the optimal condition for the maximum production of C{sub 10}-C{sub 17} was successfully calculated.

  8. Kinetic modeling of hydrocracking reaction in a trickle-bed reactor with Pt/Y-zeolite catalysts

    International Nuclear Information System (INIS)

    Lee, BalSang; Park, Myung-June; Kim, Young-A; Park, Eun Duck; Han, Jeongsik; Jeong, Kwang-Eun; Kim, Chul-Ung; Jeong, Soon-Yong

    2014-01-01

    A kinetic model is developed to predict the entire distribution of hydrocarbon products for the hydrocracking reaction with Pt/Y-zeolite catalysts in a trickle-bed reactor. Operating conditions, such as temperature, pressure, and wax and H 2 flow rates were varied to evaluate their effects on conversion and distribution, and kinetic parameters were estimated using the experimental data that covers the window of operating conditions. The comparison between experimental data and simulated results corroborated the validity of the developed model, and the quantitative prediction of the reactor performance was clearly demonstrated. To make evident the usefulness of the model, an optimization method, genetic algorithm (GA), was applied, and the optimal condition for the maximum production of C 10 -C 17 was successfully calculated

  9. Characterization and kinetic study of Diels-Alder reaction: Detailed study on N-phenylmaleimide and furan based benzoxazine with potential self-healing application

    Directory of Open Access Journals (Sweden)

    Z. Stirn

    2016-07-01

    Full Text Available The Diels-Alder reaction between N-phenylmaleimide and benzoxazine bearing furan group was investigated for the purpose of successful appliance of self-healing in benzoxazine polymer networks. The reaction as a function of temperature/time was performed in molten state and in a solution, where also the kinetic study was performed. The Diels-Alder reaction leads to a mixture of two diastereomers: endo presented at lower cyclo-reversion temperature and exo at higher. Therefore, the conversion rates and exo/endo ratio were studied in detail for both systems. For instance, in molten state the Diels-Alder reaction was triggered by the temperature of the melting point at 60 °C with exo/endo ratio preferable to the endo adduct. The study of the kinetics in a solution revealed that the Diels-Alder reaction followed typical bimolecular reversible second-order reaction. The activation energies were close to the previous literature data; 48.4 and 51.9 kJ·mol–1 for Diels-Alder reaction, and 91.0 and 102.3 kJ·mol–1 for retro-Diels-Alder reaction, in acetonitrile and chloroform, respectively. The reaction equilibrium in a solution is much more affected by the retro-Diels-Alder reaction than in a molten state. This study shows detailed investigation of DA reaction and provides beneficial knowledge for further use in self-healing polymer networks.

  10. Kinetic and mechanisms of methanimine reactions with singlet and triplet molecular oxygen: Substituent and catalyst effects

    Science.gov (United States)

    Asgharzadeh, Somaie; Vahedpour, Morteza

    2018-06-01

    Methanimine reaction with O2 on singlet and triplet potential energy surfaces are investigated using B3PW91, M06-2X, MP2 and CCSD(T) methods. Thermodynamic and kinetic parameters are calculated at M06-2X method. The most favorable channel involves H-abstraction of CH2NH+O2 to the formation of HCN + H2O2 products via low level energy barrier. The catalytic effect of water molecule on HCN + H2O2 products pathway are investigated. Result shows that contribution of water molecule using complex formation with methanimine can decreases barrier energy of transition state and the reaction rate increases. Also, substituent effect of fluorine atom as deactivating group are investigated on the main reaction pathway.

  11. Discovery of a Significant Acetone•Hydroperoxy Adduct Chaperone Effect and Its Impact on the Determination of Room Temperature Rate Constants for Acetonylperoxy/Hydroperoxy Self-Reactions and Cross Reaction Via Infrared Kinetic Spectroscopy.

    Science.gov (United States)

    Grieman, F. J.; Hui, A. O.; Okumura, M.; Sander, S. P.

    2017-12-01

    In order to model the upper troposphere/lower stratosphere in regions containing acetone properly, the kinetics of the acetonylperoxy/hydroperoxy self-reactions and cross reaction have been studied over a wide temperature range using Infrared Kinetic Spectroscopy. We report here the determination of different rate constants for the acetonylperoxy chemistry that we obtained at 298 K compared to currently accepted values. A considerable increase in the observed HO2 self-reaction rate constant due to rate enhancement via the chaperone effect from the reaction between HO2 and the (CH3)2CO•HO2 hydrogen-bonded adduct, even at room temperature, was discovered that was previously ignored. Correct determination of the acetonylperoxy and hydroperoxy kinetics must include this dependence of the HO2 self-reaction rate on acetone concentration. Via excimer laser flash photolysis to create the radical reactants, HO2 absorption was monitored in the infrared by diode laser wavelength modulation detection simultaneously with CH3C(O)CH2O2absorption monitored in the ultraviolet at 300 nm as a function of time. Resulting decay curves were fit concurrently first over a short time scale to obtain the rate constants minimizing subsequent product reactions. Modeling/fitting with a complete reaction scheme was then performed to refine the rate constants and test their veracity. Experiments were carried out over a variety of concentrations of acetone and methanol. Although no effect due to methanol concentration was found at room temperature, the rate constant for the hydroperoxy self-reaction was found to increase linearly with acetone concentration which is interpreted as the adduct being formed and resulting in a chaperone mechanism that enhances the self-reaction rate: (CH3)2CO·HO2 + HO2 → H2O2 + O2 + (CH3)2CO Including this effect, the resulting room temperature rate constants for the cross reaction and the acetonylperoxy self-reaction were found to be 2-3 times smaller than

  12. The reaction kinetics of amino radicals with sulfur dioxide

    DEFF Research Database (Denmark)

    Gao, Yide; Glarborg, Peter; Marshall, Paul

    2015-01-01

    Application of the laser photolysis-laser-induced fluorescence method to the reaction NH2+SO2 in argon bath gas yields pressure-dependent, third-order kinetics which may be summarized as k = (1.49 ± 0.15) × 10-31 (T/298 K)-0.83cm6 molecule-2 s-1 over 292-555K, where the uncertainty is the 95......% confidence interval and includes possible systematic errors. The quenching of vibrationally excited NH2 is consistent with a high-pressure limit for NH2+SO2 of (1.62 ± 0.25) × 10-11cm3 molecule-1 s-1 over the temperature range 295-505K, where again the 95% confidence interval is shown. Ab initio analysis...... yields a H2N-SO2 dissociation enthalpy of 73.5 kJ mol-1, and comparison with RRKM theory and the exponential down model for energy transfer yields down = 350 cm-1 for Ar at room temperature....

  13. Kinetic mechanism for modeling of electrochemical reactions.

    Science.gov (United States)

    Cervenka, Petr; Hrdlička, Jiří; Přibyl, Michal; Snita, Dalimil

    2012-04-01

    We propose a kinetic mechanism of electrochemical interactions. We assume fast formation and recombination of electron donors D- and acceptors A+ on electrode surfaces. These mediators are continuously formed in the electrode matter by thermal fluctuations. The mediators D- and A+, chemically equivalent to the electrode metal, enter electrochemical interactions on the electrode surfaces. Electrochemical dynamics and current-voltage characteristics of a selected electrochemical system are studied. Our results are in good qualitative agreement with those given by the classical Butler-Volmer kinetics. The proposed model can be used to study fast electrochemical processes in microsystems and nanosystems that are often out of the thermal equilibrium. Moreover, the kinetic mechanism operates only with the surface concentrations of chemical reactants and local electric potentials, which facilitates the study of electrochemical systems with indefinable bulk.

  14. 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.

  15. DNA effects upon the reaction between acetonitrile pentacyanoferrate (II) and ruthenium pentammine pyrazine: Kinetic and thermodynamic evidence of the interaction of DNA with anionic species

    International Nuclear Information System (INIS)

    Grueso, E.; Prado-Gotor, R.; Lopez, M.; Gomez-Herrera, C.; Sanchez, F.

    2005-01-01

    The kinetics of the reaction between ruthenium pentaammine pyrazine and acetonitrile pentacyanoferrate (II) to obtain the binuclear anionic complex [Fe(CN) 5 pzRu(NH 3 ) 5 ] - , and the reverse (dissociation) process, have been studied in solutions containing DNA. The results corresponding to this reaction and those corresponding to the reverse (dissociation) process show a clear influence of DNA on their kinetics. The results can be interpreted using a modified Pseudophase Model. From the results obtained for the dissociation reaction one can conclude that the binuclear anionic complex [Fe(CN) 5 pzRu(NH 3 ) 5 ] - interacts with DNA

  16. Studies on the ruthenium complexes. IX. Kinetic studies on the deaquation-anation reaction of aquapentaammineruthenium(III) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Ohyoshi, A; Hiraki, S I; Odate, T; Kohata, S; Oda, J [Kumamoto Univ. (Japan). Faculty of Engineering

    1975-01-01

    The deaquation-anation reaction of (Ru(OH/sub 2/)(NH/sub 3/)/sub 5/)X/sub 3/-type complexes in the solid state, as shown by the (Ru(OH/sub 2/)(NH/sub 3/)/sub 5/)X/sub 3/(s)..-->..(RuX(NH/sub 3/)/sub 5/)X/sub 2/(s)+H/sub 2/O(g) equation, where X is Cl, Br, I, and NO/sub 3/ respectively, was kinetically studied by means of thermogravimetry (TG) along with differential thermal analysis (DTA). The activation energy and entropy in the reaction process (Esub(a) kcal/mol, ..delta..S c.u.) are, respectively, found by isothermal kinetic study to be (22.7, - 7.1) for the chloride, (23.4, - 5.2) for the bromide, (26.7, 5.8) for the iodide, and (19.3 - 15.9) for the nitrate. The reaction seems to proceed through the following two steps, except in the case of the iodide: (Ru(OH/sub 2/)(NH/sub 3/)/sub 5/)X/sub 3/..-->..(RuX(OH/sub 2/)(NH/sub 3/)/sub 5/)X/sub 2/..-->..(RuX(NH/sub 3/)/sub 5/)X/sub 2/+H/sub 2/O. The first step is regarded as the rate-determining one.

  17. Kinetic and thermodynamic study of the reaction catalyzed by glucose-6-phosphate dehydrogenase with nicotinamide adenine dinucleotide

    International Nuclear Information System (INIS)

    Martin del Campo, Julia S.; Patino, Rodrigo

    2011-01-01

    Research highlights: → The reaction catalyzed by one enzyme of the pentose phosphate pathway was studied. → A spectrophotometric method is proposed for kinetic and thermodynamic analysis. → The pH and the temperature influences are reported on physical chemical properties. → Relative concentrations of substrates are also important in the catalytic process. - Abstract: The enzyme glucose-6-phosphate dehydrogenase (G6PD, EC 1.1.1.49) from Leuconostoc mesenteroides has a dual coenzyme specificity with oxidized nicotinamide adenine dinucleotide (NAD ox ) and oxidized nicotinamide adenine dinucleotide phosphate as electron acceptors. The G6PD coenzyme selection is determined by the metabolic cellular prevailing conditions. In this study a kinetic and thermodynamic analysis is presented for the reaction catalyzed by G6PD from L. mesenteroides with NAD ox as coenzyme in phosphate buffer. For this work, an in situ spectrophotometric technique was employed based on the detection of one product of the reaction. Substrate and coenzyme concentrations as well as temperature and pH effects were evaluated. The apparent equilibrium constant, the Michaelis constant, and the turnover number were determined as a function of each experimental condition. The standard transformed Gibbs energy of reaction was determined from equilibrium constants at different initial conditions. For the product 6-phospho-D-glucono-1,5-lactone, a value of the standard Gibbs energy of formation is proposed, Δ f G o = -1784 ± 5 kJ mol -1 .

  18. Kinetic and thermodynamic study of the reaction catalyzed by glucose-6-phosphate dehydrogenase with nicotinamide adenine dinucleotide

    Energy Technology Data Exchange (ETDEWEB)

    Martin del Campo, Julia S. [Departamento de Fisica Aplicada, Centro de Investigacion y de Estudios Avanzados - Unidad Merida, Carretera antigua a Progreso Km. 6, A.P. 73 Cordemex, 97310, Merida, Yucatan (Mexico); Patino, Rodrigo, E-mail: rtarkus@mda.cinvestav.mx [Departamento de Fisica Aplicada, Centro de Investigacion y de Estudios Avanzados - Unidad Merida, Carretera antigua a Progreso Km. 6, A.P. 73 Cordemex, 97310, Merida, Yucatan (Mexico)

    2011-04-20

    Research highlights: {yields} The reaction catalyzed by one enzyme of the pentose phosphate pathway was studied. {yields} A spectrophotometric method is proposed for kinetic and thermodynamic analysis. {yields} The pH and the temperature influences are reported on physical chemical properties. {yields} Relative concentrations of substrates are also important in the catalytic process. - Abstract: The enzyme glucose-6-phosphate dehydrogenase (G6PD, EC 1.1.1.49) from Leuconostoc mesenteroides has a dual coenzyme specificity with oxidized nicotinamide adenine dinucleotide (NAD{sub ox}) and oxidized nicotinamide adenine dinucleotide phosphate as electron acceptors. The G6PD coenzyme selection is determined by the metabolic cellular prevailing conditions. In this study a kinetic and thermodynamic analysis is presented for the reaction catalyzed by G6PD from L. mesenteroides with NAD{sub ox} as coenzyme in phosphate buffer. For this work, an in situ spectrophotometric technique was employed based on the detection of one product of the reaction. Substrate and coenzyme concentrations as well as temperature and pH effects were evaluated. The apparent equilibrium constant, the Michaelis constant, and the turnover number were determined as a function of each experimental condition. The standard transformed Gibbs energy of reaction was determined from equilibrium constants at different initial conditions. For the product 6-phospho-D-glucono-1,5-lactone, a value of the standard Gibbs energy of formation is proposed, {Delta}{sub f}G{sup o} = -1784 {+-} 5 kJ mol{sup -1}.

  19. Assessment of sorption properties and kinetic reaction of phosphorus reactive material to limit diffuse pollution

    Directory of Open Access Journals (Sweden)

    Bus Agnieszka

    2017-09-01

    Full Text Available Assessment of sorption properties and kinetic reaction of phosphorus reactive material to limit diffuse pollution. Polonite® is an effective reactive material (manufactured from opoka rock for removing phosphorus from aqueous solutions. In conducted experiments, Polonite® of grain size of 2–5 mm was used as a potential reactive material which can be used as a filter fulfillment to reduce phosphorus diffuse pollution from agriculture areas. Kinetic and equilibrium studies (performed as a batch experiment were carried out as a function of time to evaluate the sorption properties of the material. The obtained results show that Polonite® effectively removes such contamination. All tested concentrations (0.998, 5.213, 10.965 mg P-PO4·L−1 are characterized by a better fit to pseudo-second kinetic order. The Langmuir isotherm the best reflects the mechanism of adsorption process in case of Polonite® and based on the isotherm, calculated maximum adsorption capacity equals 96.58 mg P-PO4·g−1.

  20. Influence of crystal defects on the chemical reactivity of recoil atoms in oxygen-containing chromium compounds

    International Nuclear Information System (INIS)

    Costea, T.

    1969-01-01

    The influence of crystal defects on the chemical reactivity of recoil atoms produced by the reaction 50 Cr (n,γ) 51 Cr in oxygen-containing chromium compounds has been studied. Three methods have been used to introduce the defects: doping (K 2 CrO 4 doped with BaCrO 4 ), irradiation by ionizing radiation (K 2 CrO 4 irradiated in the presence of Li 2 CO 3 ) and non-stoichiometry (the semi-conducting oxides of the CrO 3 -Cr 2 O 3 series). The thermal annealing kinetics of the irradiated samples have been determined, and the activation energy has been calculated. In all cases it has been observed that there is a decrease in the activation energy for thermal annealing in the presence of the defects. In order to explain the annealing process, an electronic mechanism has been proposed based on the interaction between the recoil species and the charge-carriers (holes or electrons). (author) [fr

  1. Kinetics of the Reactions of IO Radicals with NO and NO2

    Science.gov (United States)

    Daykin, E. P.; Wine, P. H.

    1997-01-01

    A laser flash photolysis-long path absorption technique has been employed to study the kinetics of the reactions of IO radicals with NO and NO2 as a function of temperature and pressure. The IO and NO rate coefficient is independent of pressure over the range 40-200 Torr of N2, and its temperature dependence over the range 242-359 K is adequately described by the Arrhenius expression k(sub 1) = (6.9 +/- 1.7) x 10(exp -12) exp[(328 +/- 71)/T] cu cm/(molecule.s) (errors are 2 sigma, precision only). These Arrhenius parameters are similar to those determined previously for the ClO + NO and BrO + NO reactions. The IO and NO2 association reaction is found to be in the falloff regime over the temperature and pressure ranges investigated (254-354 K and 40-750 Torr of N2). Assuming F(sub c) = 0.4 independent of temperature, a physically reasonable set of falloff parameters which adequately describe the data are k(sub 0) = 7.7 x 10(exp -31)(T/300)(exp -5.0) cm(exp 6)/(molecule(exp 2).s) and k(sub infinity) = 1.55 x 10(exp -11)cu cm/(molecule.s) independent of temperature. The IO + NO2 rate coefficients determined in this study are about a factor of 2 faster than those reported in the only previous study of this reaction.

  2. Dynamic Model of Basic Oxygen Steelmaking Process Based on Multi-zone Reaction Kinetics: Model Derivation and Validation

    Science.gov (United States)

    Rout, Bapin Kumar; Brooks, Geoff; Rhamdhani, M. Akbar; Li, Zushu; Schrama, Frank N. H.; Sun, Jianjun

    2018-04-01

    A multi-zone kinetic model coupled with a dynamic slag generation model was developed for the simulation of hot metal and slag composition during the basic oxygen furnace (BOF) operation. The three reaction zones (i) jet impact zone, (ii) slag-bulk metal zone, (iii) slag-metal-gas emulsion zone were considered for the calculation of overall refining kinetics. In the rate equations, the transient rate parameters were mathematically described as a function of process variables. A micro and macroscopic rate calculation methodology (micro-kinetics and macro-kinetics) were developed to estimate the total refining contributed by the recirculating metal droplets through the slag-metal emulsion zone. The micro-kinetics involves developing the rate equation for individual droplets in the emulsion. The mathematical models for the size distribution of initial droplets, kinetics of simultaneous refining of elements, the residence time in the emulsion, and dynamic interfacial area change were established in the micro-kinetic model. In the macro-kinetics calculation, a droplet generation model was employed and the total amount of refining by emulsion was calculated by summing the refining from the entire population of returning droplets. A dynamic FetO generation model based on oxygen mass balance was developed and coupled with the multi-zone kinetic model. The effect of post-combustion on the evolution of slag and metal composition was investigated. The model was applied to a 200-ton top blowing converter and the simulated value of metal and slag was found to be in good agreement with the measured data. The post-combustion ratio was found to be an important factor in controlling FetO content in the slag and the kinetics of Mn and P in a BOF process.

  3. Kinetic isotope effect studies of the S-adenosylmethionine synthetase reaction

    International Nuclear Information System (INIS)

    Markham, G.D.; Parkin, D.W.; Schramm, V.L.

    1986-01-01

    S-adenosylmethionine (AdoMet) synthetase catalyzes a unique substitution reaction at the 5' carbon of MgATP. Kinetic isotope effect (V/K) measurements have been used to investigate the mechanism of AdoMet synthetase from E. coli. Changes in 3 H/ 14 C ratios when AdoMet is formed from a mixture of either ([5'- 14 C]ATP and [5'- 12 C,1'- 3 H]ATP) or ([5'- 3 H]ATP and [5'- 1 H,1'- 14 C]ATP) were examined. The effects of varying the concentrations of the co-substrate methionine and the monovalent cation activator K + were investigated. Substitution of 14 C for 12 C at the 5' position of ATP yields a primary V/K kinetic isotope effect ( 12 C/ 14 C) of 1.128 +/- 0.004 at low K + and methionine concentrations. The observed isotope effect diminishes slightly to 1.107 +/- 0.003 when both K + and methionine are present at saturating concentrations, suggesting that MgATP has only a low commitment to catalysis from at conditions near Vmax. No secondary V/K 3 H isotope effect from [5'- 3 H]ATP was detected ( 1 H/ 3 H) = 0.997 +/- 0.003. The magnitude of the primary 14 C isotope effect and the small secondary 3 H effect demonstrate that AdoMet synthesis occurs with a S/sub N/ 2 transition state which is symmetric with respect to the sulfur nucleophile and the departing tripolyphosphate group

  4. Laboratory Studies of Stratospheric Bromine Chemistry: Kinetics of the Reactions of Bromine Monoxide with Nitrogen Dioxide and Atomic Oxygen.

    Science.gov (United States)

    Thorn, Robert Peyton, Jr.

    A laser flash photolysis - long path absorption technique has been employed to study the kinetics of the reaction rm BrO + NO_2 + M{k _{16}atopto} products as a function of temperature (248-346 K), pressure (16 -800 Torr), and buffer gas identity (rm N _2,CF_4). 351 nm photolysis of rm NO_2/Br_2/N_2 mixtures generated BrO. The BrO decay in the presence of excess NO_2 was followed by UV absorption at 338.3 nm. The reaction is in the falloff regime between third and second order over the entire range of conditions investigated. This is the first study where temperature dependent measurements of k_{16} (P,T) have been reported at pressures greater than 12 Torr; hence, these results help constrain choices of k_{16}(P,T) for use in modeling stratospheric BrO_{rm x} chemistry. The kinetics of the important stratospheric reaction rm BrO+O(^3P)_sp{to }{k_{14}}Br+O_2 in N_2 buffer gas have been studied as a function of temperature (233-328 K) and pressure (25 -150 Torr) using a novel dual laser flash photolysis/long path absorption/resonance fluorescence technique. 248 nm pulsed laser photolysis of rm Br_2/O _3/N_2 mixtures produces O atoms in excess over Br_2. After a delay sufficient for BrO to be generated, a 532 nm laser pulse photolyses a small fraction of the O_3 to generate O(^3P). The decay of O(^3P) in the presence of an excess, known concentration of BrO, as determined by UV absorption at 338.3 nm and by numerical simulation, is then followed by time-resolved atomic resonance fluorescence spectroscopy. The experimental results have shown the reaction kinetics to be independent of pressure, to increase with decreasing temperature, and to be faster than suggested by the only previous (indirect) measurement. The resulting Anhenius expression for k_{14}(T) is given below.rm k_{14 }(T) = 1.64times 10^{-11} exp (263/T) cm^3 molecule ^{-1} s^{-1} The absolute accuracy of k_{14 }(T) at any temperature within the range studied is estimated to be +/-25%. Possible kinetic

  5. Kinetics and

    Directory of Open Access Journals (Sweden)

    Mojtaba Ahmadi

    2016-11-01

    Full Text Available The aqueous degradation of Reactive Yellow 84 (RY84 by potassium peroxydisulfate (K2S2O8 has been studied in laboratory scale experiments. The effect of the initial concentrations of potassium peroxydisulfate and RY84, pH and temperature on RY84 degradation were also examined. Experimental data were analyzed using first and second-order kinetics. The degradation kinetics of RY84 of the potassium peroxydisulfate process followed the second-order reaction kinetics. These rate constants have an extreme values similar to of 9.493 mM−1min−1 at a peroxydisulfate dose of 4 mmol/L. Thermodynamic parameters such as activation (Ea and Gibbs free energy (ΔG° were also evaluated. The negative value of ΔGo and Ea shows the spontaneous reaction natural conditions and exothermic nature.

  6. Oxidation of fluoroquinolone antibiotics and structurally related amines by chlorine dioxide: Reaction kinetics, product and pathway evaluation.

    Science.gov (United States)

    Wang, Pei; He, Yi-Liang; Huang, Ching-Hua

    2010-12-01

    Fluoroquinolones (FQs) are a group of widely prescribed antibiotics and have been frequently detected in the aquatic environment. The reaction kinetics and transformation of seven FQs (ciprofloxacin (CIP), enrofloxacin (ENR), norfloxacin (NOR), ofloxacin (OFL), lomefloxacin (LOM), pipemidic acid (PIP) and flumequine (FLU)) and three structurally related amines (1-phenylpiperazine (PP), N-phenylmorpholine (PM) and 4-phenylpiperidine (PD)) toward chlorine dioxide (ClO(2)) were investigated to elucidate the behavior of FQs during ClO(2) disinfection processes. The reaction kinetics are highly pH-dependent, can be well described by a second-order kinetic model incorporating speciation of FQs, and follow the trend of OFL > ENR > CIP ∼ NOR ∼ LOM > > PIP in reactivity. Comparison among FQs and related amines and product characterization indicate that FQs' piperazine ring is the primary reactive center toward ClO(2). ClO(2) likely attacks FQ's piperazinyl N4 atom followed by concerted fragmentation involving piperazinyl N1 atom, leading to dealkylation, hydroxylation and intramolecular ring closure at the piperazine moiety. While FQs with tertiary N4 react faster with ClO(2) than FQs with secondary N4, the overall reactivity of the piperazine moiety also depends strongly on the quinolone ring through electronic effects. The reaction rate constants obtained in clean water matrix can be used to model the decay of CIP by ClO(2) in surface water samples, but overestimate the decay in wastewater samples. Overall, transformation of FQs, particularly for those with tertiary N4 amines, could be expected under typical ClO(2) disinfection conditions. However, the transformation may not eliminate antibacterial activity because of little destruction at the quinolone ring. Copyright © 2010 Elsevier Ltd. All rights reserved.

  7. Kinetics of the high-temperature combustion reactions of dibutylether using composite computational methods

    KAUST Repository

    Rachidi, Mariam El

    2015-01-01

    This paper investigates the high-temperature combustion kinetics of n-dibutyl ether (n-DBE), including unimolecular decomposition, H-abstraction by H, H-migration, and C{single bond}C/C{single bond}O β-scission reactions of the DBE radicals. The energetics of H-abstraction by OH radicals is also studied. All rates are determined computationally using the CBS-QB3 and G4 composite methods in conjunction with conventional transition state theory. The B3LYP/6-311++G(2df,2pd) method is used to optimize the geometries and calculate the frequencies of all reactive species and transition states for use in ChemRate. Some of the rates calculated in this study vary markedly from those obtained for similar reactions of alcohols or alkanes, particularly those pertaining to unimolecular decomposition and β-scission at the α-β C{single bond}C bond. These variations show that analogies to alkanes and alcohols are, in some cases, inappropriate means of estimating the reaction rates of ethers. This emphasizes the need to establish valid rates through computation or experimentation. Such studies are especially important given that ethers exhibit promising biofuel and fuel additive characteristics. © 2014.

  8. Removal of triclosan via peroxidases-mediated reactions in water: Reaction kinetics, products and detoxification

    International Nuclear Information System (INIS)

    Li, Jianhua; Peng, Jianbiao; Zhang, Ya; Ji, Yuefei; Shi, Huanhuan; Mao, Liang; Gao, Shixiang

    2016-01-01

    Highlights: • Enzymatic treatment of triclosan in water by soybean and horseradish peroxidases. • pH, H_2O_2 concentration and enzyme dosage affected the removal efficiency of TCS. • The removal of TCS by SBP was more efficient than that of HRP. • K_C_A_T and K_C_A_T/K_M values for SBP toward TCS were much higher than those for HRP. • Polymers formed via radical coupling mechanism were nontoxic to the growth of alga. - Abstract: This study investigated and compared reaction kinetics, product characterization, and toxicity variation of triclosan (TCS) removal mediated by soybean peroxidase (SBP), a recognized potential peroxidase for removing phenolic pollutants, and the commonly used horseradish peroxidase (HRP) with the goal of assessing the technical feasibility of SBP-catalyzed removal of TCS. Reaction conditions such as pH, H_2O_2 concentration and enzyme dosage were found to have a strong influence on the removal efficiency of TCS. SBP can retain its catalytic ability to remove TCS over broad ranges of pH and H_2O_2 concentration, while the optimal pH and H_2O_2 concentration were 7.0 and 8 μM, respectively. 98% TCS was removed with only 0.1 U mL"−"1 SBP in 30 min reaction time, while an HRP dose of 0.3 U mL"−"1 was required to achieve the similar conversion. The catalytic performance of SBP towards TCS was more efficient than that of HRP, which can be explained by catalytic rate constant (K_C_A_T) and catalytic efficiency (K_C_A_T/K_M) for the two enzymes. MS analysis in combination with quantum chemistry computation showed that the polymerization products were generated via C−C and C−O coupling pathways. The polymers were proved to be nontoxic through growth inhibition of green alga (Scenedesmus obliquus). Taking into consideration of the enzymatic treatment cost, SBP may be a better alternative to HRP upon the removal and detoxification of TCS in water/wastewater treatment.

  9. 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.

  10. UV-visible spectrum of the phenyl radical and kinetics of its reaction with NO in the gas phase

    DEFF Research Database (Denmark)

    Wallington, T.J.; Egsgaard, H.; Nielsen, O.J.

    1998-01-01

    Pulse radiolysis transient UV-visible absorption spectroscopy was used to study the UV-visible absorption spectrum (225-575 nm) of the phenyl radical, C6H5(.), and kinetics of its reaction with NO. Phenyl radicals have a strong broad featureless absorption in the region of 225-340 nm...

  11. Kinetics and mechanism of the furan peroxide formation in the reaction of furfural with hydrogen peroxide in the presence and absence of sodium molybdate

    International Nuclear Information System (INIS)

    Grunskaya, E.P.; Badovskaya, L.A.; Kaklyugina, T.Ya.; Poskonin, V.V.

    2000-01-01

    Kinetics of the initial stage of the reaction of furfural with hydrogen peroxide are studied in the presence of Na 2 MoO 4 in water and without catalytic additions in n-butanol. Organic peroxide having in its disposal Mo(6), which is the only product on the initial stage of the reaction, is formed since the first minutes of oxidation of furfural by hydrogen peroxide with the presence of Na 2 MoO 4 . The mechanisms of conversion of furfural in the Na 2 MoO 4 - H 2 O system and its oxidation by peroxide without sodium molybdate are discussed. Schemes of formation of furfural complexes based on the results of kinetic studies are suggested. Comparison of obtained data demonstrates that presence of the sodium molybdates in the reaction medium trends to change of reaction procedure in the hydrogen peroxide [ru

  12. Kinetics on the reaction of 6-chloroquinoline and p-substituted benzoylchlorides under high pressures

    International Nuclear Information System (INIS)

    Kim, Eung Ryul; Lim, Jong Wan; Kim, Se Kyong; Ko, Young Shin

    2002-01-01

    The reactions rates of substituted 6-chloroquinoline, with p-substituted benzoyichlorides (p-CH 3 , p-H, p-NO 2 ) have been measured by conductometry in acetonitrile, and the rate constants are determined at various temperatures (10,15,20,25 .deg. C) and pressures (1, 200, 500, 1000 bar). From the values of rate constants, the activation parameters (Ea, ΔV ≠ , ΔH ≠ , ΔS ≠ , and ΔG ≠ ) and the pressure dependence of Hammett ρ values were determined. The rate constants increased with increasing temperatures and pressures, and are further increased to introduction to the electron donor substituents in substrate (p-NO 2 ) with 6-chloroquinoline. When, the activation volume and the activation entropy are all negative. And the Hammett ρ values are positive for the substrate over the pressure and temperature range studied. The results of kinetic studies for pressure and substituent show that thease reactions proceed in typical S N 2 reaction mechanism and 'associative S N 2' in bond formation favored with increasing pressures

  13. Steady-state isotopic transient kinetic analysis investigation of CO-O2 and CO-NO reactions over a commercial automotive catalyst

    International Nuclear Information System (INIS)

    Oukaci, R.; Blackmond, D.G.; Goodwin, J.G. Jr.; Gallaher, G.R.

    1992-01-01

    In this paper, steady-state isotopic transient kinetic analysis (SSITKA) is used to study two model reactions, CO oxidation and CO-NO reactions, on a typical formulation of a three-way auto-catalyst. Under steady-state conditions, abrupt switches in the isotopic composition of CO ( 12 C 16 O/ 13 C 18 O) were carried out to produce isotopic transients in both labeled reactants and products. Along with the determination of the average surface lifetimes and concentrations of reaction intermediates, an analysis of the transient responses along the carbon reaction pathway indicated that the distribution of active sites for the formation of CO 2 was bimodal for both reactions. Furthermore, relatively few surface sites contributed to the overall reaction rate

  14. The influence of adsorbate interactions on elementary reaction kinetics : CO with NO, N, O, or H on Rh(100)

    NARCIS (Netherlands)

    Jansen, M.M.M.

    2010-01-01

    The kinetics of heterogeneously catalysed reactions is often described by highly simplified models. For example, the reacting adsorbates occupy one kind of site, surfaces do not reconstruct and lateral interactions between adsorbates are often neglected. Particularly the latter is only allowed for

  15. The efficiency of driving chemical reactions by a physical non-equilibrium is kinetically controlled.

    Science.gov (United States)

    Göppel, Tobias; Palyulin, Vladimir V; Gerland, Ulrich

    2016-07-27

    An out-of-equilibrium physical environment can drive chemical reactions into thermodynamically unfavorable regimes. Under prebiotic conditions such a coupling between physical and chemical non-equilibria may have enabled the spontaneous emergence of primitive evolutionary processes. Here, we study the coupling efficiency within a theoretical model that is inspired by recent laboratory experiments, but focuses on generic effects arising whenever reactant and product molecules have different transport coefficients in a flow-through system. In our model, the physical non-equilibrium is represented by a drift-diffusion process, which is a valid coarse-grained description for the interplay between thermophoresis and convection, as well as for many other molecular transport processes. As a simple chemical reaction, we consider a reversible dimerization process, which is coupled to the transport process by different drift velocities for monomers and dimers. Within this minimal model, the coupling efficiency between the non-equilibrium transport process and the chemical reaction can be analyzed in all parameter regimes. The analysis shows that the efficiency depends strongly on the Damköhler number, a parameter that measures the relative timescales associated with the transport and reaction kinetics. Our model and results will be useful for a better understanding of the conditions for which non-equilibrium environments can provide a significant driving force for chemical reactions in a prebiotic setting.

  16. Kinetic Models Study of Hydrogenation of Aromatic Hydrocarbons in Vacuum Gas Oil and Basrah Crude Oil Reaction

    Directory of Open Access Journals (Sweden)

    Muzher M. Ibraheem

    2013-05-01

    Full Text Available             The aim of this research is to study the kinetic reaction models for catalytic hydrogenation of aromatic content for Basrah crude oil (BCO and vacuum gas oil (VGO derived from Kirkuk crude oil which has the boiling point rang of (611-833K.            This work is performed using a hydrodesulphurization (HDS pilot plant unit located in AL-Basil Company. A commercial (HDS catalyst cobalt-molybdenum (Co-Mo supported in alumina (γ-Al2O3 is used in this work. The feed is supplied by North Refinery Company in Baiji. The reaction temperatures range is (600-675 K over liquid hourly space velocity (LHSV range of (0.7-2hr-1 and hydrogen pressure is 3 MPa with H2/oil ratio of 300 of Basrah Crude oil (BCO, while the corresponding conditions for vacuum gas oil (VGO are (583-643 K, (1.5-3.75 hr-1, 3.5 MPa and 250  respectively .            The results showed that the reaction kinetics is of second order for both types of feed. Activation energies are found to be 30.396, 38.479 kJ/mole for Basrah Crude Oil (BCO and Vacuum Gas Oil (VGO respectively.

  17. Two-scale large deviations for chemical reaction kinetics through second quantization path integral

    International Nuclear Information System (INIS)

    Li, Tiejun; Lin, Feng

    2016-01-01

    Motivated by the study of rare events for a typical genetic switching model in systems biology, in this paper we aim to establish the general two-scale large deviations for chemical reaction systems. We build a formal approach to explicitly obtain the large deviation rate functionals for the considered two-scale processes based upon the second quantization path integral technique. We get three important types of large deviation results when the underlying two timescales are in three different regimes. This is realized by singular perturbation analysis to the rate functionals obtained by the path integral. We find that the three regimes possess the same deterministic mean-field limit but completely different chemical Langevin approximations. The obtained results are natural extensions of the classical large volume limit for chemical reactions. We also discuss its implication on the single-molecule Michaelis–Menten kinetics. Our framework and results can be applied to understand general multi-scale systems including diffusion processes. (paper)

  18. Evaluation of reaction mechanisms and the kinetic parameters for the transesterification of castor oil by liquid enzymes

    DEFF Research Database (Denmark)

    Andrade, Thalles Allan; Errico, Massimiliano; Christensen, Knud Villy

    2017-01-01

    of the transesterification of castor oil with methanol using the enzyme Eversa® Transform as catalyst were investigated. Reactions were carried out for 8 hours at 35 °C with: an alcohol-to-oil molar ratio equal to 6:1, a 5 wt% of liquid enzyme solution and addition of 5 wt% of water by weight of castor oil. From...... methanolysis rates of glycerides obtained, indicated that transesterification dominates over hydrolysis. The mechanism among the four models proposed that gave the best fit could be simplified, eliminating the kinetic parameters with negligible effects on the reaction rates. This model was able to fit...

  19. Kinetics and Products of the Reactions of Fluorine Atoms with ClNO and Br2 from 295 to 950 K.

    Science.gov (United States)

    Bedjanian, Yuri

    2017-11-09

    The kinetics and products of the reactions of F atoms with Br 2 and ClNO have been studied in a flow reactor coupled with an electron impact ionization mass spectrometer at nearly 2 Torr total pressure of helium and over a wide temperature range, T = 295-950 K. The rate constant of the reaction F + ClNO → products (1) was determined under pseudo-first order conditions, monitoring the kinetics of F atom consumption in excess of ClNO. The measured temperature independent rate constant, k 1 = (1.29 ± 0.13) × 10 -10 cm 3 molecule -1 s -1 (T = 299-950 K), was found to be in excellent agreement with the only previous low temperature study which allowed to recommend the value of k 1 in an extended temperature range, 228-950 K. FCl and Cl atoms were observed as the reactions products (corresponding to two reaction pathways: Cl-atom abstraction and replacement with fluorine atom, respectively) with the independent of temperature, in the range 295-948 K, yields of 0.68 ± 0.10 and 0.32 ± 0.05, respectively. Rate constant of the reaction F + Br 2 (2), k 2 = (1.28 ± 0.20) × 10 -10 cm 3 molecule -1 s -1 , determined using both absolute and relative rate methods, was found to be independent of temperature at T = 299-940 K.

  20. Periodontal tissue reaction to customized nano-hydroxyapatite block scaffold in one-wall intrabony defect: a histologic study in dogs.

    Science.gov (United States)

    Lee, Jung-Seok; Park, Weon-Yeong; Cha, Jae-Kook; Jung, Ui-Won; Kim, Chang-Sung; Lee, Yong-Keun; Choi, Seong-Ho

    2012-04-01

    This study evaluated histologically the tissue responses to and the effects of a customized nano-hydroxyapatite (n-HA) block bone graft on periodontal regeneration in a one-wall periodontal-defect model. A customized block bone for filling in the standardized periodontal defect was fabricated from prefabricated n-HA powders and a polymeric sponge. Bilateral 4×4×5 mm (buccolingual width×mesiodistal width×depth), one-wall, critical-size intrabony periodontal defects were surgically created at the mandibular second and fourth premolars of five Beagle dogs. In each dog, one defect was filled with block-type HA and the other served as a sham-surgery control. The animals were sacrificed following an 8-week healing interval for clinical and histological evaluations. Although the sites that received an n-HA block showed minimal bone formation, the n-HA block was maintained within the defect with its original hexahedral shape. In addition, only a limited inflammatory reaction was observed at sites that received an n-HA block, which might have been due to the high stability of the customized block bone. In the limitation of this study, customized n-HA block could provide a space for periodontal tissue engineering, with minimal inflammation.

  1. The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

    KAUST Repository

    Ebner, Davidâ C.; Bagdanoff, Jeffreyâ T.; Ferreira, Ericâ M.; McFadden, Ryanâ M.; Caspi, Danielâ D.; Trend, Raissaâ M.; Stoltz, Brianâ M.

    2009-01-01

    The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 degrees C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-to-excellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones.

  2. The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

    KAUST Repository

    Ebner, Davidâ C.

    2009-12-07

    The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 degrees C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-to-excellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones.

  3. Analyzing General Chemistry Texts' Treatment of Rates of Change Concepts in Reaction Kinetics Reveals Missing Conceptual Links

    Science.gov (United States)

    Seethaler, Sherry; Czworkowski, John; Wynn, Lynda

    2018-01-01

    Change over time is a crosscutting theme in the sciences that is pivotal to reaction kinetics, an anchoring concept in undergraduate chemistry, and students' struggles with rates of change are well-documented. Informed by the education scholarship in chemistry, physics, and mathematics, a research team with members from complementary disciplinary…

  4. Aerobic composting of waste activated sludge: Kinetic analysis for microbiological reaction and oxygen consumption

    International Nuclear Information System (INIS)

    Yamada, Y.; Kawase, Y.

    2006-01-01

    In order to examine the optimal design and operating parameters, kinetics for microbiological reaction and oxygen consumption in composting of waste activated sludge were quantitatively examined. A series of experiments was conducted to discuss the optimal operating parameters for aerobic composting of waste activated sludge obtained from Kawagoe City Wastewater Treatment Plant (Saitama, Japan) using 4 and 20 L laboratory scale bioreactors. Aeration rate, compositions of compost mixture and height of compost pile were investigated as main design and operating parameters. The optimal aerobic composting of waste activated sludge was found at the aeration rate of 2.0 L/min/kg (initial composting mixture dry weight). A compost pile up to 0.5 m could be operated effectively. A simple model for composting of waste activated sludge in a composting reactor was developed by assuming that a solid phase of compost mixture is well mixed and the kinetics for microbiological reaction is represented by a Monod-type equation. The model predictions could fit the experimental data for decomposition of waste activated sludge with an average deviation of 2.14%. Oxygen consumption during composting was also examined using a simplified model in which the oxygen consumption was represented by a Monod-type equation and the axial distribution of oxygen concentration in the composting pile was described by a plug-flow model. The predictions could satisfactorily simulate the experiment results for the average maximum oxygen consumption rate during aerobic composting with an average deviation of 7.4%

  5. Effect of noise on defect chaos in a reaction-diffusion model.

    Science.gov (United States)

    Wang, Hongli; Ouyang, Qi

    2005-06-01

    The influence of noise on defect chaos due to breakup of spiral waves through Doppler and Eckhaus instabilities is investigated numerically with a modified Fitzhugh-Nagumo model. By numerical simulations we show that the noise can drastically enhance the creation and annihilation rates of topological defects. The noise-free probability distribution function for defects in this model is found not to fit with the previously reported squared-Poisson distribution. Under the influence of noise, the distributions are flattened, and can fit with the squared-Poisson or the modified-Poisson distribution. The defect lifetime and diffusive property of defects under the influence of noise are also checked in this model.

  6. Dual kinetic curves in reversible electrochemical systems.

    Directory of Open Access Journals (Sweden)

    Michael J Hankins

    Full Text Available We introduce dual kinetic chronoamperometry, in which reciprocal relations are established between the kinetic curves of electrochemical reactions that start from symmetrical initial conditions. We have performed numerical and experimental studies in which the kinetic curves of the electron-transfer processes are analyzed for a reversible first order reaction. Experimental tests were done with the ferrocyanide/ferricyanide system in which the concentrations of each component could be measured separately using the platinum disk/gold ring electrode. It is shown that the proper ratio of the transient kinetic curves obtained from cathodic and anodic mass transfer limited regions give thermodynamic time invariances related to the reaction quotient of the bulk concentrations. Therefore, thermodynamic time invariances can be observed at any time using the dual kinetic curves for reversible reactions. The technique provides a unique possibility to extract the non-steady state trajectory starting from one initial condition based only on the equilibrium constant and the trajectory which starts from the symmetrical initial condition. The results could impact battery technology by predicting the concentrations and currents of the underlying non-steady state processes in a wide domain from thermodynamic principles and limited kinetic information.

  7. Kinetic Studies on Enzyme-Catalyzed Reactions: Oxidation of Glucose, Decomposition of Hydrogen Peroxide and Their Combination

    Science.gov (United States)

    Tao, Zhimin; Raffel, Ryan A.; Souid, Abdul-Kader; Goodisman, Jerry

    2009-01-01

    The kinetics of the glucose oxidase-catalyzed reaction of glucose with O2, which produces gluconic acid and hydrogen peroxide, and the catalase-assisted breakdown of hydrogen peroxide to generate oxygen, have been measured via the rate of O2 depletion or production. The O2 concentrations in air-saturated phosphate-buffered salt solutions were monitored by measuring the decay of phosphorescence from a Pd phosphor in solution; the decay rate was obtained by fitting the tail of the phosphorescence intensity profile to an exponential. For glucose oxidation in the presence of glucose oxidase, the rate constant determined for the rate-limiting step was k = (3.0 ± 0.7) ×104 M−1s−1 at 37°C. For catalase-catalyzed H2O2 breakdown, the reaction order in [H2O2] was somewhat greater than unity at 37°C and well above unity at 25°C, suggesting different temperature dependences of the rate constants for various steps in the reaction. The two reactions were combined in a single experiment: addition of glucose oxidase to glucose-rich cell-free media caused a rapid drop in [O2], and subsequent addition of catalase caused [O2] to rise and then decrease to zero. The best fit of [O2] to a kinetic model is obtained with the rate constants for glucose oxidation and peroxide decomposition equal to 0.116 s−1 and 0.090 s−1 respectively. Cellular respiration in the presence of glucose was found to be three times as rapid as that in glucose-deprived cells. Added NaCN inhibited O2 consumption completely, confirming that oxidation occurred in the cellular mitochondrial respiratory chain. PMID:19348778

  8. Kinetics of oxygen reduction reaction at tin-adatoms-modified gold electrodes in acidic media

    International Nuclear Information System (INIS)

    Miah, Md. Rezwan; Ohsaka, Takeo

    2009-01-01

    In the present report, oxygen reduction reaction (ORR) at polycrystalline gold (Au (poly)) electrode in situ modified by the underpotential deposition (upd) of Sn-adatoms is addressed. The ORR was investigated at the Sn-adatoms-modified Au (poly) electrode by the hydrodynamic voltammetric technique with a view to evaluating the various related kinetic parameters. The results demonstrated that the underpotential deposited Sn-adatoms on the Au (poly) electrode substantially promoted the activity of the electrode towards an exclusive one-step four-electron ORR forming H 2 O as the final product.

  9. Kinetics of oxygen reduction reaction at tin-adatoms-modified gold electrodes in acidic media

    Energy Technology Data Exchange (ETDEWEB)

    Miah, Md. Rezwan [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)], E-mail: mrmche@yahoo.com; Ohsaka, Takeo [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)], E-mail: ohsaka@echem.titech.ac.jp

    2009-10-01

    In the present report, oxygen reduction reaction (ORR) at polycrystalline gold (Au (poly)) electrode in situ modified by the underpotential deposition (upd) of Sn-adatoms is addressed. The ORR was investigated at the Sn-adatoms-modified Au (poly) electrode by the hydrodynamic voltammetric technique with a view to evaluating the various related kinetic parameters. The results demonstrated that the underpotential deposited Sn-adatoms on the Au (poly) electrode substantially promoted the activity of the electrode towards an exclusive one-step four-electron ORR forming H{sub 2}O as the final product.

  10. Point defects and atomic transport in crystals

    International Nuclear Information System (INIS)

    Lidiard, A.B.

    1981-02-01

    There are two principle aspects to the theory of atomic transport in crystals as caused by the action of point defects, namely (1) the calculation of relevant properties of the point defects (energies and other thermodynamic characteristics of the different possible defects, activation energies and other mobility parameters) and (2) the statistical mechanics of assemblies of defects, both equilibrium and non-equilibrium assemblies. In the five lectures given here both these aspects are touched on. The first two lectures are concerned with the calculation of relevant point defect properties, particularly in ionic crystals. The first lecture is more general, the second is concerned particularly with some recent calculations of the free volumes of formation of defects in various ionic solids; these solve a rather long-standing problem in this area. The remaining three lectures are concerned with the kinetic theory of defects mainly in relaxation, drift and diffusion situations

  11. The first experimental confirmation of the fractional kinetics containing the complex-power-law exponents: Dielectric measurements of polymerization reactions

    Science.gov (United States)

    Nigmatullin, R. R.; Arbuzov, A. A.; Salehli, F.; Giz, A.; Bayrak, I.; Catalgil-Giz, H.

    2007-01-01

    For the first time we achieved incontestable evidence that the real process of dielectric relaxation during the polymerization reaction of polyvinylpyrrolidone (PVP) is described in terms of the fractional kinetic equations containing complex-power-law exponents. The possibility of the existence of the fractional kinetics containing non-integer complex-power-law exponents follows from the general theory of dielectric relaxation that has been suggested recently by one of the authors (R.R.N). Based on the physical/geometrical meaning of the fractional integral with complex exponents there is a possibility to develop a general theory of dielectric relaxation based on the self-similar (fractal) character of the reduced (averaged) microprocesses that take place in the mesoscale region. This theory contains some essential predictions related to existence of the non-integer power-law kinetics and the results of this paper can be considered as the first confirmation of existence of the kinetic phenomena that are described by fractional derivatives with complex-power-law exponents. We want to stress here that with the help of a new complex fitting function for the complex permittivity it becomes possible to describe the whole process for real and imaginary parts simultaneously throughout the admissible frequency range (30 Hz-13 MHz). The fitting parameters obtained for the complex permittivity function for three temperatures (70, 90 and 110 °C) confirm in general the picture of reaction that was known qualitatively before. They also reveal some new features, which improve the interpretation of the whole polymerization process. We hope that these first results obtained in the paper will serve as a good stimulus for other researches to find the traces of the existence of new fractional kinetics in other relaxation processes unrelated to the dielectric relaxation. These results should lead to the reconsideration and generalization of irreversibility and kinetic phenomena that

  12. Nucleation of voids and other irradiation-produced defect aggregates

    International Nuclear Information System (INIS)

    Wiedersich, H.; Katz, J.L.

    1976-01-01

    The nucleation of defect clusters in crystalline solids from radiation-produced defects is different from the usual nucleation processes in one important aspect: the condensing defects, interstitial atoms and vacancies, can mutually annihilate and are thus similar to matter and antimatter. The nucleation process is described as the simultaneous reaction of vacancies and interstitials (and gas atoms if present) with embryos of all sizes. The reaction rates for acquisition of point defects (and gas atoms) are calculated from their respective jump frequencies and concentrations in the supersaturated system. The reaction rates for emission of point defects are derived from the free energies of the defect clusters in the thermodynamic equilibrium system, i.e., the system without excess point defects. This procedure differs from that used in conventional nucleation theory and permits the inclusion of the ''antimatter'' defect into the set of reaction-rate equations in a straightforward manner. The method is applied to steady-state nucleation, during irradiation, of both dislocation loops and voids in the absence and in the presence of immobile and mobile gas. The predictions of the nucleation theory are shown to be in qualitative agreement with experimental observations, e.g., void densities increase with increasing displacement rates; gases such as helium enhance void nucleation; at low displacement rates and at high temperatures the presence of gas is essential to void formation. For quantitative predictions, the theory must be extended to include the termination of nucleation

  13. Kinetic mechanism of molecular energy transfer and chemical reactions in low-temperature air-fuel plasmas.

    Science.gov (United States)

    Adamovich, Igor V; Li, Ting; Lempert, Walter R

    2015-08-13

    This work describes the kinetic mechanism of coupled molecular energy transfer and chemical reactions in low-temperature air, H2-air and hydrocarbon-air plasmas sustained by nanosecond pulse discharges (single-pulse or repetitive pulse burst). The model incorporates electron impact processes, state-specific N(2) vibrational energy transfer, reactions of excited electronic species of N(2), O(2), N and O, and 'conventional' chemical reactions (Konnov mechanism). Effects of diffusion and conduction heat transfer, energy coupled to the cathode layer and gasdynamic compression/expansion are incorporated as quasi-zero-dimensional corrections. The model is exercised using a combination of freeware (Bolsig+) and commercial software (ChemKin-Pro). The model predictions are validated using time-resolved measurements of temperature and N(2) vibrational level populations in nanosecond pulse discharges in air in plane-to-plane and sphere-to-sphere geometry; temperature and OH number density after nanosecond pulse burst discharges in lean H(2)-air, CH(4)-air and C(2)H(4)-air mixtures; and temperature after the nanosecond pulse discharge burst during plasma-assisted ignition of lean H2-mixtures, showing good agreement with the data. The model predictions for OH number density in lean C(3)H(8)-air mixtures differ from the experimental results, over-predicting its absolute value and failing to predict transient OH rise and decay after the discharge burst. The agreement with the data for C(3)H(8)-air is improved considerably if a different conventional hydrocarbon chemistry reaction set (LLNL methane-n-butane flame mechanism) is used. The results of mechanism validation demonstrate its applicability for analysis of plasma chemical oxidation and ignition of low-temperature H(2)-air, CH(4)-air and C(2)H(4)-air mixtures using nanosecond pulse discharges. Kinetic modelling of low-temperature plasma excited propane-air mixtures demonstrates the need for development of a more accurate

  14. Mass Transfer and Chemical Reaction Approach of the Kinetics of the Acetylation of Gadung Flour using Glacial Acetic Acid

    Directory of Open Access Journals (Sweden)

    Andri Cahyo Kumoro

    2015-03-01

    Full Text Available Acetylation is one of the common methods of modifying starch properties by introducing acetil (CH3CO groups to starch molecules at low temperatures. While most acetylation is conducted using starch as anhidroglucose source and acetic anhydride or vinyl acetate as nucleophilic agents, this work employ reactants, namely flour and glacial acetic acid. The purpose of this work are to study the effect of pH reaction and GAA/GF mass ratio on the rate of acetylation reaction and to determine its rate constants. The acetylation of gadung flour with glacial acetic acid in the presence of sodium hydroxide as a homogenous catalyst was studied at ambient temperature with pH ranging from 8-10 and different mass ratio of acetic acid : gadung flour (1:3; 1:4; and 1:5. It was found that increasing pH, lead to increase the degree of substitution, while increasing GAA/GF mass ratio caused such decreases in the degree of substitution, due to the hydrolysis of the acetylated starch. The desired starch acetylation reaction is accompanied by undesirable hydrolysis reaction of the acetylated starch after 40-50 minutes reaction time. Investigation of kinetics of the reaction observed that the value of mass transfer rate constant (Kcs is smaller than the surface reaction rate constant (k. Thus, it can be concluded that rate controlling step is mass transfer.  © 2015 BCREC UNDIP. All rights reservedReceived: 7th August 2014; Revised: 8th September 2014; Accepted: 14th September 2014How to Cite: Kumoro, A.C., Amelia, R. (2015. Mass Transfer and Chemical Reaction Approach of the Kinetics of the Acetylation of Gadung Flour using Glacial Acetic Acid. Bulletin of Chemical Reaction Engineering & Catalysis, 10 (1: 30-37. (doi:10.9767/bcrec.10.1.7181.30-37Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.1.7181.30-37

  15. Defect engineering: design tools for solid state electrochemical devices

    International Nuclear Information System (INIS)

    Tuller, Harry L.

    2003-01-01

    The interest in solid state electrochemical devices including sensors, fuel cells, batteries, oxygen permeation membranes, etc. has grown rapidly in recent years. Many of the same figures of merit apply to these different applications, the key ones being ionic conduction in solid electrolytes, mixed ionic-electronic conduction (MIEC) in electrodes and permeation membranes, and gas-solid reaction kinetics in sensors and fuel cells. Optimization of device performance often relies on the careful understanding and control of both ionic and electronic defects in the materials that make up the key device components. To date, most materials in use have been discovered serendipitously. A key focus of this paper is on the tools available to scientists and engineers to practice 'defect engineering' for the purpose of optimizing the performance of such materials. Dopants, controlled structural disorder, and interfaces are examined in relation to increasing the conductivity of solid electrolytes. The creation of defect bands is demonstrated as a means for introducing high levels of electronic conductivity into a solid electrolyte for the purpose of creating a mixed conductor and thereby a monolithic fuel cell structure. Dopants are also examined as a means of reducing losses in a high temperature resonant sensor platform. The control of microstructure, down to the nano-scale, is shown capable of inverting the predominant ionic to an electronic charge carrier and thereby markedly modifying electrical properties. Electrochemical bias and light are also discussed in terms of creating defects locally thereby providing means for micromachining a broad range of materials with precise dimensional control, low residual stress and controlled etch rates

  16. Chemical kinetics and oil shale process design

    Energy Technology Data Exchange (ETDEWEB)

    Burnham, A.K.

    1993-07-01

    Oil shale processes are reviewed with the goal of showing how chemical kinetics influences the design and operation of different processes for different types of oil shale. Reaction kinetics are presented for organic pyrolysis, carbon combustion, carbonate decomposition, and sulfur and nitrogen reactions.

  17. Analysis of chemical reaction kinetics of depredating organic pollutants from secondary effluent of wastewater treatment plant in constructed wetlands.

    Science.gov (United States)

    Wang, Hao; Jiang, Dengling; Yang, Yong; Cao, Guoping

    2013-01-01

    Four subsurface constructed wetlands were built to treat the secondary effluent of a wastewater treatment plant in Tangshan, China. The chemical pollutant indexes of chemical oxygen demand (COD) were analyzed to evaluate the removal efficiency of organic pollutants from the secondary effluent of the wastewater treatment plant. In all cases, the subsurface constructed wetlands were efficient in treating organic pollutants. Under the same hydraulic loading condition, the horizontal flow wetlands exhibited better efficiency of COD removal than vertical flow wetlands: the removal rates in horizontal flow wetlands could be maintained at 68.4 ± 2.42% to 92.2 ± 1.61%, compared with 63.8 ± 1.19% to 85.0 ± 1.25% in the vertical flow wetlands. Meanwhile, the chemical reaction kinetics of organic pollutants was analyzed, and the results showed that the degradation courses of the four subsurface wetlands all corresponded with the first order reaction kinetics to a large extent.

  18. An experimental and theoretical kinetic study of the reaction of OH radicals with tetrahydrofuran

    KAUST Repository

    Giri, Binod

    2016-06-24

    Tetrahydrofuran (CHO, THF) and its alkylated derivatives of the cyclic ether family are considered to be promising future biofuels. They appear as important intermediates during the low-temperature oxidation of conventional hydrocarbon fuels and of heavy biofuels such as long-chain fatty acid methyl esters. The reaction of tetrahydrofuran with OH radicals was investigated in a shock tube, over a temperature range of 800-1340 K and at pressures near 1.5 bar. Hydroxyl radicals were generated by the rapid thermal decomposition of tert-butyl hydroperoxide, and a UV laser absorption technique was used to monitor the mole fraction of OH radicals. High-level CCSD(T)/cc-pV(D,T)Z//MP2/aug-cc-pVDZ quantum chemical calculations were performed to explore the chemistry of the THF+OH reaction system. Our calculations reveal that the THF+OH (R1) reaction proceeds via either direct or indirect H-abstraction from various sites, leading to the formation of tetrahydrofuran-2-yl (THF-R2) or tetrahydrofuran-3-yl (THF-R3) radicals and water. Theoretical kinetic analysis revealed that both channels are important under conditions relevant to combustion. To our knowledge, this is the first direct experimental and theoretical kinetic study of the reaction of tetrahydrofuran with OH radicals at high temperatures. The following theoretical rate expressions (in units of cmmols) are recommended for combustion modeling in the temperature range 800-1350 K: . k1(T)=4.11×1040.16em0ex(TK)2.69exp(1316.80.16em0exKT)2.em0ex0.16em0ex(THF+OH→Products) . k2(T)=6.930.16em0ex×10110.16em0ex(TK)0.41exp(-106.80.16em0exKT)2.em0ex0.16em0ex(THF+OH→THF-R20.16em0ex+H2O) . k3(T)=4.120.16em0ex×1030.16em0ex(TK)3.02exp(456.90.16em0exKT)2.em0ex0.16em0ex(THF+OH→THF-R30.16em0ex+H2O) . .

  19. The kinetics of the photochemical reaction cycle of deuterated bacteriorhodopsin and pharaonis halorhodopsin

    International Nuclear Information System (INIS)

    Szakacs, Julianna; Lakatos, Melinda; Varo, Gy.; Ganea, Constanta

    2005-01-01

    Kinetic isotope effects in the photochemical reaction cycle of bacteriorhodopsin and pharaonis halorhodopsin were determined in H 2 O and D 2 O at normal pH, to get insight in the proton dependent steps of the transport process. All the steps of the bacteriorhodopsin photocycle at normal pH exhibited a strong isotope effect. In the case of halorhodopsin in both the chloride and nitrate transporting conditions the photocycle was not strongly affected by the deuterium exchange. In the case of chloride, a slight slow down of the photocycle could be observed. On the opposite, in the nitrate transport conditions a reverse effect is present. (author)

  20. Pre-recombination quenching of the radiation induced fluorescence as the approach to study kinetics of ion-molecular reactions

    International Nuclear Information System (INIS)

    Borovkov, V.I.; Ivanishko, I.S.

    2011-01-01

    This study deals with the geminate ion recombination in the presence of bulk scavengers, that is the so-called scavenger problem, as well as with the effect of the scavenging reaction on the radiation-induced recombination fluorescence. have proposed a method to determine the rate constant of the bulk reaction between neutral scavengers and one of the geminate ions if the ion-molecular reaction prevented the formation of electronically excited states upon recombination involving a newly formed ion. If such pre-recombination quenching of the radiation-induced fluorescence took place, it manifested itself as a progressive decrease in the decay of the fluorescence intensity. The relative change in the fluorescence decay as caused by the scavengers was believed to be closely related to the kinetics of the scavenging reaction. The goal of the present study is to support this method, both computationally and experimentally because there are two factors, which cast doubt on the intuitively obvious approach to the scavenger problem: spatial correlations between the particles involved and the drift of the charged reagent in the electric field of its geminate partner. Computer simulation of geminate ions recombination with an explicit modeling of the motion trajectories of scavengers has been performed for media of low dielectric permittivity, i.e. for the maximal Coulomb interaction between the ions. The simulation has shown that upon continuous diffusion of the particles involved, the joint effect of the two above factors can be considered as insignificant with a high accuracy. Besides, it is concluded then that the method of pre-recombination quenching could be applied to study parallel and consecutive reactions where the yields of excited states in the reaction pathways are different with the use of very simple analytical relations of the formal chemical kinetics. The conclusion has been confirmed experimentally by the example of the reactions of electron transfer from

  1. Temperature dependence of carbon kinetic isotope effect for the oxidation reaction of ethane by OH radicals under atmospherically relevant conditions

    Science.gov (United States)

    Piansawan, Tammarat; Saccon, Marina; Laumer, Werner; Gensch, Iulia; Kiendler-Scharr, Astrid

    2015-04-01

    Modeling of the global distribution of atmospheric ethane sources and sinks by using the 13C isotopic composition requires accurate knowledge of the carbon kinetic isotope effect (KIE) of its atmospheric removal reactions. The quantum mechanical prediction implies the necessity to elucidate the temperature dependence of KIE within atmospherically relevant temperature range by experiment. In this study, the KIE and its temperature dependence for ethane oxidation by OH radicals was investigated at ambient pressure in a temperature range of 243 K to 303 K. The chemical reactions were carried out in a 15 L PFE reaction chamber, suspended in a thermally controlled oven. The isotope ratios of the gas phase components during the course of the reactions were measured by Thermal Desorption -- Gas Chromatography -- Isotope Ratio Mass Spectrometry (TD-GC-IRMS). For each temperature, the KIE was derived from the temporal evolution of the concentration and stable carbon isotope ratio (δ13C) of ethane using a method adapted from the relative reaction rate concept. The room temperature KIE of the ethane reaction with OH radicals was found to be 6.85 ± 0.32 ‰. This value is in agreement with the previously reported value of 8.57 ± 1.95 ‰ [Anderson et al. 2004] but has a substantially lower uncertainty. The experimental results will be discussed with the KIE temperature dependence predicted by quantum mechanical calculations. Reference: Rebecca S. Anderson, Lin Huang, Richard Iannone, Alexandra E. Thompson, and Jochen Rudolph (2004), Carbon Kinetic Isotope Effects in the Gas Phase Reactions of Light Alkanes and Ethene with the OH Radical at 296 ± 4 K, J. Phys. Chem. A, 108, 11537--11544

  2. 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

  3. Reaction kinetics aspect of U3O8 kernel with gas H2 on the characteristics of activation energy, reaction rate constant and O/U ratio of UO2 kernel

    International Nuclear Information System (INIS)

    Damunir

    2007-01-01

    The reaction kinetics aspect of U 3 O 8 kernel with gas H 2 on the characteristics of activation energy, reaction rate constant and O/U ratio of UO 2 kernel had been studied. U 3 O 8 kernel was reacted with gas H 2 in a reduction furnace at varied reaction time and temperature. The reaction temperature was varied at 600, 700, 750 and 850 °C with a pressure of 50 mmHg for 3 hours in gas N 2 atmosphere. The reation time was varied at 1, 2, 3 and 4 hours at a temperature of 750 °C using similar conditions. The reaction product was UO 2 kernel. The reaction kinetic aspect between U 3 O 8 and gas H 2 comprised the minimum activation energy (ΔE), the reaction rate constant and the O/U ratio of UO 2 kernel. The minimum activation energy was determined from a straight line slope of equation ln [{D b . R o {(1 - (1 - X b ) ⅓ } / (b.t.Cg)] = -3.9406 x 10 3 / T + 4.044. By multiplying with the straight line slope -3.9406 x 10 3 , the ideal gas constant (R) 1.985 cal/mol and the molarity difference of reaction coefficient 2, a minimum activation energy of 15.644 kcal/mol was obtained. The reaction rate constant was determined from first-order chemical reaction control and Arrhenius equation. The O/U ratio of UO 2 kernel was obtained using gravimetric method. The analysis result of reaction rate constant with chemical reaction control equation yielded reaction rate constants of 0.745 - 1.671 s -1 and the Arrhenius equation at temperatures of 650 - 850 °C yielded reaction rate constants of 0.637 - 2.914 s -1 . The O/U ratios of UO 2 kernel at the respective reaction rate constants were 2.013 - 2.014 and the O/U ratios at reaction time 1 - 4 hours were 2.04 - 2.011. The experiment results indicated that the minimum activation energy influenced the rate constant of first-order reaction and the O/U ratio of UO 2 kernel. The optimum condition was obtained at reaction rate constant of 1.43 s -1 , O/U ratio of UO 2 kernel of 2.01 at temperature of 750 °C and reaction time of 3

  4. Multiresponse modelling of the caramelisation reaction

    OpenAIRE

    Quintas, Mafalda; Guimarães, Carla; Baylina, João; Brandão, Teresa R. S.; Silva, Cristina L.M.

    2007-01-01

    Multiresponse modelling is a powerful tool for studying complex kinetics of reactions occurring in food products. This modelling technique uses information of reactants and products involved, allowing insightful kinetic parameters estimation and helping in clarifying reaction mechanisms. One example of a complex reaction that occurs in food processing is the caramelisation reaction. Caramelisation is the common name for a group of reactions observed when carbohydrates are exposed to high temp...

  5. Studies of ruthenium complexes, 8. Kinetic studies of the thermal substitution reaction of hexaammine and cis--dihalogenotetraammineruthenium(III) complexes in the solid state

    Energy Technology Data Exchange (ETDEWEB)

    Ohyoshi, A; Hiraki, S; Odate, T; Kohata, S; Oda, J [Kumamoto Univ. (Japan). Faculty of Engineering

    1975-01-01

    The kinetics of the thermal substitution reaction of hexaamineruthenium (III) halides and cis-dihalogenotetraamineruthenium (III) halides have been studied in the solid state. The reaction rates and kinetic parameters were determined for these two reactions; (Ru(NH/sub 3/)/sub 6/)X/sub 3/..-->..(RuX(NH/sub 3/)/sub 5/)X/sub 2/+NH/sub 3/, (X=Br, I) and cis - (RuX/sub 2/(NH/sub 3/)/sub 4/)X..-->..(RuX/sub 3/(NH/sub 3/)/sub 3/)+NH/sub 3/, (X=Cl, Br). The values of the rate constant, the activation energy, and the activation entropy were 2.10x10/sup -5/ s/sup -1/ (at 161/sup 0/C), 23.2 kcal mol/sup -1/, and -29.3 e.u. for the hexaamine bromide, and 2.92x10/sup -5/ s/sup -1/ (at 162/sup 0/C), 31.3 kcal mol/sup -1/, and -10.1 e.u. for the cis-dibromotetraamine bromide. The Ssub(N)2 mechanism is more probable for the former reaction, while the Ssub(N)1 mechanism is more probable for the latter reaction.

  6. Fixation and reduction of uranium by natural organic matter: reaction mechanisms and kinetics

    International Nuclear Information System (INIS)

    Nakashima, S.; Perruchot, A.; Trichet, J.; Disnar, J.R.

    1987-01-01

    The reactivity of lignite towards soluble uranyl species in an aqueous medium is experimentally investigated as a function of temperature (between 20 0 C and 400 0 C). The fixation process starts near 45 0 C, with reduction beginning around 120 0 C. The fixation process leads to the formation of chemically and thermally stable organo-uranyl species. The reduction of free uranyl species is accompanied by a stoichiometric (2:1) liberation of protons into the medium. These protons originate from the organic matter which thus undergoes dehydrogenation. The general evolution of the carbonaceous residue in the course of this reaction shows that alcoholic and aliphatic hydrocarbon groups are responsible for the reduction. This chemical dehydrogenation could explain the low hydrogen content of natural organic materials associated with uraniferous deposits. The kinetics of the reduction step have been studied at 180 0 C, 190 0 C and 200 0 C. The kinetic parameters determined over this temperature range, and the extrapolation made to 20 0 C, show that reduction can be a crucial process in the geochemical behaviour of uranium especially in the thermal conditions in which sedimentary basins evolve [fr

  7. Removal of triclosan via peroxidases-mediated reactions in water: Reaction kinetics, products and detoxification

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jianhua; Peng, Jianbiao [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China); Zhang, Ya [Nanjing Institute of Environmental Sciences, Ministry of Environmental Protection of the People’s Republic of China, Nanjing 210042 (China); Ji, Yuefei [College of Resources and Environmental Science, Nanjing Agricultural University, Nanjing 210095 (China); Shi, Huanhuan; Mao, Liang [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China); Gao, Shixiang, E-mail: ecsxg@nju.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China)

    2016-06-05

    Highlights: • Enzymatic treatment of triclosan in water by soybean and horseradish peroxidases. • pH, H{sub 2}O{sub 2} concentration and enzyme dosage affected the removal efficiency of TCS. • The removal of TCS by SBP was more efficient than that of HRP. • K{sub CAT} and K{sub CAT}/K{sub M} values for SBP toward TCS were much higher than those for HRP. • Polymers formed via radical coupling mechanism were nontoxic to the growth of alga. - Abstract: This study investigated and compared reaction kinetics, product characterization, and toxicity variation of triclosan (TCS) removal mediated by soybean peroxidase (SBP), a recognized potential peroxidase for removing phenolic pollutants, and the commonly used horseradish peroxidase (HRP) with the goal of assessing the technical feasibility of SBP-catalyzed removal of TCS. Reaction conditions such as pH, H{sub 2}O{sub 2} concentration and enzyme dosage were found to have a strong influence on the removal efficiency of TCS. SBP can retain its catalytic ability to remove TCS over broad ranges of pH and H{sub 2}O{sub 2} concentration, while the optimal pH and H{sub 2}O{sub 2} concentration were 7.0 and 8 μM, respectively. 98% TCS was removed with only 0.1 U mL{sup −1} SBP in 30 min reaction time, while an HRP dose of 0.3 U mL{sup −1} was required to achieve the similar conversion. The catalytic performance of SBP towards TCS was more efficient than that of HRP, which can be explained by catalytic rate constant (K{sub CAT}) and catalytic efficiency (K{sub CAT}/K{sub M}) for the two enzymes. MS analysis in combination with quantum chemistry computation showed that the polymerization products were generated via C−C and C−O coupling pathways. The polymers were proved to be nontoxic through growth inhibition of green alga (Scenedesmus obliquus). Taking into consideration of the enzymatic treatment cost, SBP may be a better alternative to HRP upon the removal and detoxification of TCS in water

  8. Reaction of plutonium with water kinetic and equilibrium behavior of binary and ternary phases in the Pu + O + H system

    International Nuclear Information System (INIS)

    Haschke, J.M.; Hodges, A.E. III; Bixby, G.E.; Lucas, R.L.

    1983-01-01

    The kinetic and equilibrium behavior of the Pu + O + H system has been studied by measuring the production of hydrogen gas formed by a sequence of hydrolysis reactions. The kinetic dependence of the Pu + H 2 O reaction on salt concentration and temperature has been defined. The metal is quantitatively converted to a fine black powder which has been identified as plutonium monoxide monohydride, PuOH. Other hydrolysis products formed in aqueous media include a second oxide hydride, Pu 7 O 9 H 3 , and the oxides Pu 2 O 3 , Pu 7 O 12 , Pu 9 O 16 , Pu 10 O 18 , Pu 12 O 22 , and PuO 2 . Thermal decomposition products of PuOH include Pu 2 O 2 H and PuO. A tentative phase diagram for Pu + O + H is presented and structural relationships of the oxide hydrides and oxides are discussed. 10 figures, 5 tables

  9. Kinetics on the reaction of substituted quinolines and p-substituted benzoylchlorides under various pressures

    International Nuclear Information System (INIS)

    Kim, Young Cheul; Lim, Jong Wan; Choi, Sung Yong; Kim, Se Kyong

    1999-01-01

    The reaction rates of substituted quinolines(6-CH 3 C 9 H 7 N, C 9 H 7 N) with p-substituted benzoylchlorides(p-CH 3 , p-H, p-NO 2 ) have been measured by conductometry in acetonitrile, and the rate constants are determined at various temperatures (10,15, 20, 25 .deg. C) and pressures(1, 200, 500, 1000bar). From the values of rate constants, the activation parameters(Ea, ΔV ≠ , ΔS ≠ , and ΔG ≠ ) and the pressure dependence of Hammett ρ values were determined. The rate constants increase as a function of temperatures and pressures, and are further increase by introduction the electron donor substituents in nucleophile(p-CH 3 ) or electron acceptor(p-NO 2 ) substituents in substrate. The activation volume, and the activation entropy are all negative. Hammett ρ values are also negative for nucleophile (ρ X ) and positive for the substrate (ρ Y ) over the pressure range studied. The results of kinetic studies for pressure and substituent show that these reactions proceed in typical S N 2 reaction mechanism and 'associative S N 2' in which bond formation favored with increasing pressures

  10. Indistinguishability and identifiability of kinetic models for the MurC reaction in peptidoglycan biosynthesis.

    Science.gov (United States)

    Hattersley, J G; Pérez-Velázquez, J; Chappell, M J; Bearup, D; Roper, D; Dowson, C; Bugg, T; Evans, N D

    2011-11-01

    An important question in Systems Biology is the design of experiments that enable discrimination between two (or more) competing chemical pathway models or biological mechanisms. In this paper analysis is performed between two different models describing the kinetic mechanism of a three-substrate three-product reaction, namely the MurC reaction in the cytoplasmic phase of peptidoglycan biosynthesis. One model involves ordered substrate binding and ordered release of the three products; the competing model also assumes ordered substrate binding, but with fast release of the three products. The two versions are shown to be distinguishable; however, if standard quasi-steady-state assumptions are made distinguishability cannot be determined. Once model structure uniqueness is ensured the experimenter must determine if it is possible to successfully recover rate constant values given the experiment observations, a process known as structural identifiability. Structural identifiability analysis is carried out for both models to determine which of the unknown reaction parameters can be determined uniquely, or otherwise, from the ideal system outputs. This structural analysis forms an integrated step towards the modelling of the full pathway of the cytoplasmic phase of peptidoglycan biosynthesis. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

  11. Computational investigation of kinetics of cross-linking reactions in proteins: importance in structure prediction.

    Science.gov (United States)

    Bandyopadhyay, Pradipta; Kuntz, Irwin D

    2009-01-01

    The determination of protein structure using distance constraints is a new and promising field of study. One implementation involves attaching residues of a protein using a cross-linking agent, followed by protease digestion, analysis of the resulting peptides by mass spectroscopy, and finally sequence threading to detect the protein folds. In the present work, we carry out computational modeling of the kinetics of cross-linking reactions in proteins using the master equation approach. The rate constants of the cross-linking reactions are estimated using the pKas and the solvent-accessible surface areas of the residues involved. This model is tested with fibroblast growth factor (FGF) and cytochrome C. It is consistent with the initial experimental rate data for individual lysine residues for cytochrome C. Our model captures all observed cross-links for FGF and almost 90% of the observed cross-links for cytochrome C, although it also predicts cross-links that were not observed experimentally (false positives). However, the analysis of the false positive results is complicated by the fact that experimental detection of cross-links can be difficult and may depend on specific experimental conditions such as pH, ionic strength. Receiver operator characteristic plots showed that our model does a good job in predicting the observed cross-links. Molecular dynamics simulations showed that for cytochrome C, in general, the two lysines come closer for the observed cross-links as compared to the false positive ones. For FGF, no such clear pattern exists. The kinetic model and MD simulation can be used to study proposed cross-linking protocols.

  12. Kinetics of in situ combustion. SUPRI TR 91

    Energy Technology Data Exchange (ETDEWEB)

    Mamora, D.D.; Ramey, H.J. Jr.; Brigham, W.E.; Castanier, L.M.

    1993-07-01

    Oxidation kinetic experiments with various crude oil types show two reaction peaks at about 250{degree}C (482{degree}F) and 400{degree}C (725{degree}F). These experiments lead to the conclusion that the fuel during high temperature oxidation is an oxygenated hydrocarbon. A new oxidation reaction model has been developed which includes two partially-overlapping reactions: namely, low-temperature oxidation followed by high-temperature oxidation. For the fuel oxidation reaction, the new model includes the effects of sand grain size and the atomic hydrogen-carbon (H/C) and oxygen-carbon (O/C) ratios of the fuel. Results based on the new model are in good agreement with the experimental data. Methods have been developed to calculate the atomic H/C and O/C ratios. These methods consider the oxygen in the oxygenated fuel, and enable a direct comparison of the atomic H/C ratios obtained from kinetic and combustion tube experiments. The finding that the fuel in kinetic tube experiments is an oxygenated hydrocarbon indicates that oxidation reactions are different in kinetic and combustion tube experiments. A new experimental technique or method of analysis will be required to obtain kinetic parameters for oxidation reactions encountered in combustion tube experiments and field operations.

  13. Analyzing atmospheric kinetic pathways using PumpKin

    Science.gov (United States)

    Markosyan, A. H.; Luque, A.; Gordillo-Vázquez, F. J.; Ebert, U.

    2013-09-01

    In the present work we show the application of our software tool called PumpKin (pathway reduction method for plasma kinetic models) to find all principal pathways of atmospheric kinetic system, i.e. the dominant reaction sequences, in chemical reaction systems. The goal was to reduce a complex plasma chemistry model. Recent kinetic models of atmospheric chemistry, or any industrial application, contain thousands of chemical reactions and species. The main difficulty is that these reduced chemical pathways depend on timescales, electric field, temperature, pressure etc. PumpKin is a universal tool, which only requires from user the temporal profile of the densities of species and the reaction rates, as well the stoichiometric matrix of the system. Also, the user should specify the timescale of interest.

  14. Modeling of uncertainties in biochemical reactions.

    Science.gov (United States)

    Mišković, Ljubiša; Hatzimanikatis, Vassily

    2011-02-01

    Mathematical modeling is an indispensable tool for research and development in biotechnology and bioengineering. The formulation of kinetic models of biochemical networks depends on knowledge of the kinetic properties of the enzymes of the individual reactions. However, kinetic data acquired from experimental observations bring along uncertainties due to various experimental conditions and measurement methods. In this contribution, we propose a novel way to model the uncertainty in the enzyme kinetics and to predict quantitatively the responses of metabolic reactions to the changes in enzyme activities under uncertainty. The proposed methodology accounts explicitly for mechanistic properties of enzymes and physico-chemical and thermodynamic constraints, and is based on formalism from systems theory and metabolic control analysis. We achieve this by observing that kinetic responses of metabolic reactions depend: (i) on the distribution of the enzymes among their free form and all reactive states; (ii) on the equilibrium displacements of the overall reaction and that of the individual enzymatic steps; and (iii) on the net fluxes through the enzyme. Relying on this observation, we develop a novel, efficient Monte Carlo sampling procedure to generate all states within a metabolic reaction that satisfy imposed constrains. Thus, we derive the statistics of the expected responses of the metabolic reactions to changes in enzyme levels and activities, in the levels of metabolites, and in the values of the kinetic parameters. We present aspects of the proposed framework through an example of the fundamental three-step reversible enzymatic reaction mechanism. We demonstrate that the equilibrium displacements of the individual enzymatic steps have an important influence on kinetic responses of the enzyme. Furthermore, we derive the conditions that must be satisfied by a reversible three-step enzymatic reaction operating far away from the equilibrium in order to respond to

  15. Study on reaction mechanism by analysis of kinetic energy spectra of light particles and formation of final products

    Science.gov (United States)

    Giardina, G.; Mandaglio, G.; Nasirov, A. K.; Anastasi, A.; Curciarello, F.; Fazio, G.

    2018-05-01

    The sensitivity of reaction mechanism in the formation of compound nucleus (CN) by the analysis of kinetic energy spectra of light particles and of reaction products are shown. The dependence of the P CN fusion probability of reactants and W sur survival probability of CN against fission at its deexcitation on the mass and charge symmetries in the entrance channel of heavy-ion collisions, as well as on the neutron numbers is discussed. The possibility of conducting a complex program of investigations of the complete fusion by reliable ways depends on the detailed and refined methods of experimental and theoretical analyses.

  16. Enhanced hydrogen reaction kinetics of nanostructured Mg-based composites with nanoparticle metal catalysts dispersed on supports

    International Nuclear Information System (INIS)

    Yoo, Yeong; Tuck, Mark; Kondakindi, Rajender; Seo, Chan-Yeol; Dehouche, Zahir; Belkacemi, Khaled

    2007-01-01

    Hydrogen reaction kinetics of nanocrystalline MgH 2 co-catalyzed with Ba 3 (Ca 1+x Nb 2-x )O 9-δ (BCN) proton conductive ceramics and nanoparticle bimetallic catalyst of Ni/Pd dispersed on single wall carbon nanotubes (SWNTs) support has been investigated. The nanoparticle bimetallic catalysts of Ni/Pd supported by SWNTs were synthesized based on a novel polyol method using NiCl 2 .6H 2 O, PdCl 2 , NaOH and ethylene glycol (EG). The nanostructured Mg composites co-catalyzed with BCN and bimetallic supported catalysts exhibited stable hydrogen desorption capacity of 6.3-6.7 wt.% H 2 and the significant enhancement of hydrogen desorption kinetics at 230-300 deg. C in comparison to either non-catalyzed MgH 2 or the nanocomposite of MgH 2 catalyzed with BCN

  17. Effect of disorder and defects in ion-implanted semiconductors optical and photothermal characterization

    CERN Document Server

    Willardson, R K; Christofides, Constantinos; Ghibaudo, Gerard

    1997-01-01

    Defects in ion-implanted semiconductors are important and will likely gain increased importance as annealing temperatures are reduced with successive IC generations. Novel implant approaches, such as MdV implantation, create new types of defects whose origin and annealing characteristics will need to be addressed. Publications in this field mainly focus on the effects of ion implantation on the material and the modification in the implanted layer after high temperature annealing. The editors of this volume and Volume 45 focus on the physics of the annealing kinetics of the damaged layer. An overview of characterization tehniques and a critical comparison of the information on annealing kinetics is also presented. Key Features * Provides basic knowledge of ion implantation-induced defects * Focuses on physical mechanisms of defect annealing * Utilizes electrical, physical, and optical characterization tools for processed semiconductors * Provides the basis for understanding the problems caused by the defects g...

  18. Thermogravimetric analysis and kinetic study of bamboo waste treated by Echinodontium taxodii using a modified three-parallel-reactions model.

    Science.gov (United States)

    Yu, Hongbo; Liu, Fang; Ke, Ming; Zhang, Xiaoyu

    2015-06-01

    In this study, the effect of pretreatment with Echinodontium taxodii on thermal decomposition characteristics and kinetics of bamboo wastes was investigated by thermogravimetric analysis. The results showed fungal pretreatment can enhance the thermal degradation of bamboo. The negative effect of extractives in bamboo on the thermal decomposition can be decreased by the pretreatment. A modified three-parallel-reactions model based on isolated lignin was firstly proposed to study pyrolysis kinetics of bamboo lignocellulose. Kinetic analysis showed that with increasing pretreatment time fungal delignification was enhanced to transform the lignin component with high activation energy into that with low activation energy and raise the cellulose content in bamboo, making the thermal decomposition easier. These results demonstrated fungal pretreatment provided a potential way to improve thermal conversion efficiency of bamboo. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Kinetics of the reaction between plutonium (4) and neptunium (4) in nitric acid solution

    Energy Technology Data Exchange (ETDEWEB)

    Koltunov, V S; Zhuravleva, G I; Marchenko, V I

    1976-01-01

    The kinetics of the oxidation of neptunium(IV) to neptunium(V) by tetravalent plutonium ions in solutions of HNO/sub 3/ + NaNO/sub 3/ at constant (..mu.. = 2) and variable (..mu.. = 0.7-2.0) ionic strengths of the solution was investigated by a spectrophotometric method. It was established that in the range of concentrations (Np(IV)) = (4.25-10.6) x 10/sup 13/; (Pu(IV)) = (2.6-3.9)x10/sup -3/ M; (H/sup +/) 0.37-1.91 M, a first order is observed with respect to the reagents, while the order of the reaction with respect to H/sup +/ ions is equal to -3. The average value of the true rate constant of the reaction is k = 27.9+-1.3 M/sup 2/xmin/sup -1/ at ..mu..=2 and 39/sup 0/C. It was shown that with increasing analytical concentration of HNO/sub 3/ and NO/sub 3//sup -/ ions (in a mixture of HNO/sub 3/ +HClO/sub 4/), the value of K decreases. On the basis of an invetigation of the dependence of the reaction rate on the temperature in the interval 31-44.8/sup 0/, we calculated the values of the energy (E = 34.6 kcal/mole), enthalpy (..delta..H* = 34 kcal/mole), free energy (..delta..F* = 19.6 kcal/mole, entropy (..delta..S* = 49 entropy units) of activation of the reaction and the formal ionic entropy of the activated complex (PuOOHNp/sup 5 +/)*, S* = -87 entropy units. A reaction mechanism including an interaction of hydrolyzed neptunium and plutonium ions as the rate-determining step was proposed and discusses. The results obtained are compared with data for this reaction in perchloric acid wolution and for other similar redox reactions.

  20. Defect Engineering toward Atomic Co-Nx -C in Hierarchical Graphene for Rechargeable Flexible Solid Zn-Air Batteries.

    Science.gov (United States)

    Tang, Cheng; Wang, Bin; Wang, Hao-Fan; Zhang, Qiang

    2017-10-01

    Rechargeable flexible solid Zn-air battery, with a high theoretical energy density of 1086 Wh kg -1 , is among the most attractive energy technologies for future flexible and wearable electronics; nevertheless, the practical application is greatly hindered by the sluggish oxygen reduction reaction/oxygen evolution reaction (ORR/OER) kinetics on the air electrode. Precious metal-free functionalized carbon materials are widely demonstrated as the most promising candidates, while it still lacks effective synthetic methodology to controllably synthesize carbocatalysts with targeted active sites. This work demonstrates the direct utilization of the intrinsic structural defects in nanocarbon to generate atomically dispersed Co-N x -C active sites via defect engineering. As-fabricated Co/N/O tri-doped graphene catalysts with highly active sites and hierarchical porous scaffolds exhibit superior ORR/OER bifunctional activities and impressive applications in rechargeable Zn-air batteries. Specifically, when integrated into a rechargeable and flexible solid Zn-air battery, a high open-circuit voltage of 1.44 V, a stable discharge voltage of 1.19 V, and a high energy efficiency of 63% at 1.0 mA cm -2 are achieved even under bending. The defect engineering strategy provides a new concept and effective methodology for the full utilization of nanocarbon materials with various structural features and further development of advanced energy materials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Kinetics of physico-chemical processes during intensive mechanical processing of ZnO-MnO2 powder mixture

    International Nuclear Information System (INIS)

    Kakazey, M.; Vlasova, M.; Dominguez-Patino, M.; Juarez-Arellano, E.A.; Bykov, A.; Leon, I.; Siqueiros-Diaz, A.

    2011-01-01

    Experimental results of electron paramagnetic resonance spectra, X-ray diffraction, scanning electron microscopy and infrared spectroscopy demonstrate that the kinetic of the physical and chemical processes that takes place during prolonged intensive mechanical processing (MP, 0 MP >3120min) of powder mixtures of 50%wt ZnO+50%wt MnO 2 can be described as a three stage process. (1) 0 MP >30min, particles destruction, formation of superficial defects, fast increment of sample average temperature (from 290 to ∼600K) and annealing of defects with the lowest energy of activation E ac . (2) 30 MP >390min, further particle destruction, slow increment of sample average temperature (from ∼600 to ∼700K), formation and growth of a very disordered layer of β-MnO 2 around ZnO particles, dehydration of MnO 2 , formation of solid solution of Mn 2+ ions in ZnO, formation of nano-quasiamorphous states in the ZnO-MnO 2 mixture and onset of the formation of the ZnMnO 3 phase. (3) 390 MP >3120min, the sample average temperature remains constant (∼700K), the reaction is completed and the spinel ZnMnO 3 phase with a unit cell a=8.431(1) A and space group Fd3-barm is the only phase present in the sample. No ferromagnetism at room temperature was detected in this study. - Highlights: → The kinetics during mechanical processing of ZnO-MnO 2 samples is a three stage process. → First stage, reduction of crystallites size and accumulation of defects. → Second stage, nano-quasiamorphous states formation and onset of the ZnMnO 3 phase. → Third stage, complete reaction to the spinel ZnMnO 3 phase.

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

    Science.gov (United States)

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

    1988-05-01

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

  3. Selected readings in chemical kinetics

    CERN Document Server

    Back, Margaret H

    2013-01-01

    Selected Readings in Chemical Kinetics covers excerpts from 12 papers in the field of general and gas-phase kinetics. The book discusses papers on the laws of connexion between the conditions of a chemical change and its amount; on the reaction velocity of the inversion of the cane sugar by acids; and the calculation in absolute measure of velocity constants and equilibrium constants in gaseous systems. The text then tackles papers on simple gas reactions; on the absolute rate of reactions in condensed phases; on the radiation theory of chemical action; and on the theory of unimolecular reacti

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

    Science.gov (United States)

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

    2018-06-01

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

  5. Analysis of Chemical Reaction Kinetics Behavior of Nitrogen Oxide During Air-staged Combustion in Pulverized Boiler

    Directory of Open Access Journals (Sweden)

    Jun-Xia Zhang

    2016-03-01

    Full Text Available Because the air-staged combustion technology is one of the key technologies with low investment running costs and high emission reduction efficiency for the pulverized boiler, it is important to reveal the chemical reaction kinetics mechanism for developing various technologies of nitrogen oxide reduction emissions. At the present work, a three-dimensional mesh model of the large-scale four corner tangentially fired boiler furnace is established with the GAMBIT pre-processing of the FLUENT software. The partial turbulent premixed and diffusion flame was simulated for the air-staged combustion processing. Parameters distributions for the air-staged and no the air-staged were obtained, including in-furnace flow field, temperature field and nitrogen oxide concentration field. The results show that the air-staged has more regular velocity field, higher velocity of flue gas, higher turbulence intensity and more uniform temperature of flue gas. In addition, a lower negative pressure zone and lower O2 concentration zone is formed in the main combustion zone, which is conducive to the NO of fuel type reduced to N2, enhanced the effect of NOx reduction. Copyright © 2016 BCREC GROUP. All rights reserved Received: 5th November 2015; Revised: 14th January 2016; Accepted: 16th January 2016  How to Cite: Zhang, J.X., Zhang, J.F. (2016. Analysis of Chemical Reaction Kinetics Behavior of Nitrogen Oxide During Air-staged Combustion in Pulverized Boiler. Bulletin of Chemical Reaction Engineering & Catalysis, 11 (1: 100-108. (doi:10.9767/bcrec.11.1.431.100-108 Permalink/DOI: http://dx.doi.org/10.9767/bcrec.11.1.431.100-108

  6. Defect creation rates in CdTe irradiated by electrons

    International Nuclear Information System (INIS)

    Caillot, M.

    1978-01-01

    Up to now, the defect creation rates in CdTe irradiated by electrons were unknown. They have been calculated for different electron kinetic energies. As the samples studied are thick, the energy loss when the electrons penetrate the material has been taken into account. The cross-sections of Cd and Te displacements vs the depth of electron penetration were determined for different electron kinetic energies, and the defect creation rates obtained for each sublattice. These creation rates have been compared with those deduced from experiments and it was found that the experimental creation rates were lower than the calculated ones. This discrepancy can be explained in terms of creation of neutral Frenkel pairs. (Auth.)

  7. Kinetics of hydrogen isotope exchange reactions

    International Nuclear Information System (INIS)

    Gold, V.; McAdam, M.E.

    1975-01-01

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

  8. In-situ X-ray Nanocharacterization of Defect Kinetics in Chalcogenide Solar Cell Materials

    Energy Technology Data Exchange (ETDEWEB)

    Bertoni, Mariana [Arizona State Univ., Tempe, AZ (United States); Lai, Barry [Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Masser, Jorg [Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Buonassisi, Tonio [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

    2016-09-21

    ) correlate positively, and In negatively with charge collection efficiency for cells with low Ga content, both at grain boundaries and in grain cores. For cells with high Ga content, the charge collection efficiency depends to much lesser extent on the elemental distribution. The objective is three folded: (1) develop an x-ray in-situ microscopy capability to simulate growth and processing conditions, (2) apply it to elucidate performance-governing defect kinetics in chalcogenide solar cell materials, and (3) to study approaches to engineer materials from the nanoscale up. The development of these capabilities will enable experimental characterization to take place under actual processing and operating conditions and it will have impact well beyond the proposed research, enabling future studies on a large variety of materials system where electronic properties depend on underlying structural or chemical inhomogeneities.

  9. Kinetic Monte Carlo modeling of chemical reactions coupled with heat transfer.

    Science.gov (United States)

    Castonguay, Thomas C; Wang, Feng

    2008-03-28

    In this paper, we describe two types of effective events for describing heat transfer in a kinetic Monte Carlo (KMC) simulation that may involve stochastic chemical reactions. Simulations employing these events are referred to as KMC-TBT and KMC-PHE. In KMC-TBT, heat transfer is modeled as the stochastic transfer of "thermal bits" between adjacent grid points. In KMC-PHE, heat transfer is modeled by integrating the Poisson heat equation for a short time. Either approach is capable of capturing the time dependent system behavior exactly. Both KMC-PHE and KMC-TBT are validated by simulating pure heat transfer in a rod and a square and modeling a heated desorption problem where exact numerical results are available. KMC-PHE is much faster than KMC-TBT and is used to study the endothermic desorption of a lattice gas. Interesting findings from this study are reported.

  10. Biochemical toxicology studies of methomyl and its kinetic reaction with cholinesterase in rats

    International Nuclear Information System (INIS)

    Tawfik, S.M.; Abdel-Hamid, F.M.

    2001-01-01

    The effect of the pesticide methomyl on acetylcholinesterase activities in brain and blood of male rats in vivo and the kinetics involved in their reaction in vitro were studied. Also, its effect on peroxidase action of catalase in vivo was studied using 14C - formate. The results showed that methomyl is a competitive inhibitor for acetylcholinesterase and the concentration levels that caused 50% inhibition of the enzyme activity were 2.1 x 10-2 M and 1.9 x 10-4 for brain and blood- Ache, respectively. The inhibition of acetylcholinesterase activity decreased to 67.5 % at the time of appearance of toxicity symptoms. The radioactivity eliminated in both the expired air and in urine was reduced

  11. 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.

  12. Kinetics of oxygen reduction reaction at electrochemically fabricated tin-palladium bimetallic electrocatalyst in acidic media

    Energy Technology Data Exchange (ETDEWEB)

    Miah, Md. Rezwan, E-mail: mrmche@yahoo.co [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Masud, Jahangir [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Ohsaka, Takeo, E-mail: ohsaka@echem.titech.ac.j [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)

    2010-12-15

    In the present article, oxygen reduction reaction (ORR) at electrochemically fabricated tin-palladium (Sn-Pd) bimetallic electrocatalyst-modified glassy carbon (GC) electrode (Sn-Pd/GC electrode) in acidic media is addressed. Hydrodynamic voltammetric measurements were employed with a view to evaluating various kinetic parameters of the ORR at the Sn-Pd/GC electrode. The obtained results obviously demonstrated that the Sn-Pd bimetallic electrocatalyt substantially promoted the activity of the GC electrode and drove the ORR through an exclusive one-step four-electron pathway forming H{sub 2}O as the final product.

  13. Kinetics of oxygen reduction reaction at electrochemically fabricated tin-palladium bimetallic electrocatalyst in acidic media

    International Nuclear Information System (INIS)

    Miah, Md. Rezwan; Masud, Jahangir; Ohsaka, Takeo

    2010-01-01

    In the present article, oxygen reduction reaction (ORR) at electrochemically fabricated tin-palladium (Sn-Pd) bimetallic electrocatalyst-modified glassy carbon (GC) electrode (Sn-Pd/GC electrode) in acidic media is addressed. Hydrodynamic voltammetric measurements were employed with a view to evaluating various kinetic parameters of the ORR at the Sn-Pd/GC electrode. The obtained results obviously demonstrated that the Sn-Pd bimetallic electrocatalyt substantially promoted the activity of the GC electrode and drove the ORR through an exclusive one-step four-electron pathway forming H 2 O as the final product.

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

    Science.gov (United States)

    Zhang, David Yu; Winfree, Erik

    2009-12-02

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

  15. Kinetics of reactions of the Actinomadura R39 DD-peptidase with specific substrates.

    Science.gov (United States)

    Adediran, S A; Kumar, Ish; Nagarajan, Rajesh; Sauvage, Eric; Pratt, R F

    2011-01-25

    The Actinomadura R39 DD-peptidase catalyzes the hydrolysis and aminolysis of a number of small peptides and depsipeptides. Details of its substrate specificity and the nature of its in vivo substrate are not, however, well understood. This paper describes the interactions of the R39 enzyme with two peptidoglycan-mimetic substrates 3-(D-cysteinyl)propanoyl-D-alanyl-D-alanine and 3-(D-cysteinyl)propanoyl-D-alanyl-D-thiolactate. A detailed study of the reactions of the former substrate, catalyzed by the enzyme, showed DD-carboxypeptidase, DD-transpeptidase, and DD-endopeptidase activities. These results confirm the specificity of the enzyme for a free D-amino acid at the N-terminus of good substrates and indicated a preference for extended D-amino acid leaving groups. The latter was supported by determination of the structural specificity of amine nucleophiles for the acyl-enzyme generated by reaction of the enzyme with the thiolactate substrate. It was concluded that a specific substrate for this enzyme, and possibly the in vivo substrate, may consist of a partly cross-linked peptidoglycan polymer where a free side chain N-terminal un-cross-linked amino acid serves as the specific acyl group in an endopeptidase reaction. The enzyme is most likely a DD-endopeptidase in vivo. pH-rate profiles for reactions of the enzyme with peptides, the thiolactate named above, and β-lactams indicated the presence of complex proton dissociation pathways with sticky substrates and/or protons. The local structure of the active site may differ significantly for reactions of peptides and β-lactams. Solvent kinetic deuterium isotope effects indicate the presence of classical general acid/base catalysis in both acylation and deacylation; there is no evidence of the low fractionation factor active site hydrogen found previously in class A and C β-lactamases.

  16. Kinetic energy spectrum and polarization of neutrons from the reaction 12C(p,n)X at 590 MeV

    International Nuclear Information System (INIS)

    Arnold, J.

    1998-01-01

    The kinetic energy spectrum and the polarization of the PSI neutron beam produced in the reaction 12 C(p,n)X at 0 with 590 MeV polarized protons were investigated. A strong energy dependence of the neutron beam polarization is observed which was not expected at the time the neutron beam was built. (orig.)

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

    International Nuclear Information System (INIS)

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

    1982-01-01

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

  18. Redox potentials and kinetics of the Ce 3+/Ce 4+ redox reaction and solubility of cerium sulfates in sulfuric acid solutions

    Science.gov (United States)

    Paulenova, A.; Creager, S. E.; Navratil, J. D.; Wei, Y.

    Experimental work was performed with the aim of evaluating the Ce 4+/Ce 3+ redox couple in sulfuric acid electrolyte for use in redox flow battery (RFB) technology. The solubility of cerium sulfates in 0.1-4.0 M sulfuric acid at 20-60 °C was studied. A synergistic effect of both sulfuric acid concentration and temperature on the solubility of cerous sulfate was observed. The solubility of cerous sulfate significantly decreased with rising concentration of sulfuric acid and rising temperature, while the solubility of ceric sulfate goes through a significant maximum at 40 °C. Redox potentials and the kinetics of the cerous/ceric redox reaction were also studied under the same temperature-concentration conditions. The redox potentials were measured using the combined redox electrode (Pt-Ag/AgCl) in equimolar Ce 4+/Ce 3+ solutions (i.e.[Ce 3+]=[Ce 4+]) in sulfuric acid electrolyte. The Ce 3+/Ce 4+ redox potentials significantly decrease (i.e. shift to more negative values) with rising sulfuric acid concentration; a small maximum is observed at 40 °C. Cyclic voltammetric experiments confirmed slow electrochemical kinetics of the Ce 3+/Ce 4+ redox reaction on carbon glassy electrodes (CGEs) in sulfuric acid solutions. The observed dependencies of solubilities, the redox potentials and the kinetics of Ce 3+/Ce 4+ redox reaction on sulfuric acid concentration are thought to be the result of inequivalent complexation of the two redox species by sulfate anions: the ceric ion is much more strongly bound to sulfate than is the cerous ion. The best temperature-concentration conditions for the RFB electrolytes appear to be 40 °C and 1 M sulfuric acid, where the relatively good solubility of both cerium species, the maximum of redox potentials, and the more or less satisfying stability of CGE s were found. Even so, the relatively low solubility of cerium salts in sulfuric acid media and slow redox kinetics of the Ce 3+/Ce 4+ redox reaction at carbon indicate that the Ce 3+/Ce

  19. Initial deposition and electron paramagnetic resonance defects characterization of TiO2 films prepared using successive ionic layer adsorption and reaction method

    International Nuclear Information System (INIS)

    Wu Yiyong; Shi Yaping; Xu Xianbin; Sun Chengyue

    2012-01-01

    Successive ionic layer adsorption and reaction (SILAR) technique was considered promisingly to deposit ultra thin titanium dioxide (TiO 2 ) films under ambient condition. In this paper, the growth process, structures and paramagnetic defects of the films were characterized by complementary techniques of atomic force microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and electron paramagnetic resonance spectroscopy. The results indicate that on glass substrate the SILAR TiO 2 film nucleates in an island mode within the initial five deposition cycles but grows in a layer-by-layer mode afterwards. The growth rate was measured as 4.6 Å/cycle. In the as-deposited films, a kind of paramagnetic defects is detected at g (2.0029) and it can be attributed to oxygen vacancies. These as-received oxygen vacancies could be annealed out at 473 K. Ultraviolet irradiation on the as-deposited films can also decrease the density of the defects. The relative mechanisms on the phenomenon were discussed in this paper. - Highlights: ► TiO 2 films are deposited on glass at 25 °C by successive ionic layer adsorption and reaction method with a rate of 4.6 Å/cycle. ► The films nucleate in an island mode initially but grow in a layer mode afterwards. ► The SILAR TiO 2 films nucleation period is five cycles. ► Electron paramagnetic resonance spectroscopy shows that TiO 2 films paramagnetic defects are attributed to oxygen vacancies. ► They will decrease by anneal or ultraviolet radiation and form hydroxyl or superoxide radicals.

  20. Kinetics of physico-chemical processes during intensive mechanical processing of ZnO-MnO{sub 2} powder mixture

    Energy Technology Data Exchange (ETDEWEB)

    Kakazey, M.; Vlasova, M.; Dominguez-Patino, M. [CIICAp-Universidad Autonoma del Estado de Morelos, Cuernavaca (Mexico); Juarez-Arellano, E.A., E-mail: eajuarez@unpa.edu.mx [Universidad del Papaloapan, Tuxtepec, Oaxaca (Mexico); Bykov, A. [Institute for Problems of Materials Science of NASU, Kyiv (Ukraine); Leon, I. [CIQ-Universidad Autonoma del Estado de Morelos, Cuernavaca (Mexico); Siqueiros-Diaz, A. [FCQI-Universidad Autonoma del Estado de Morelos, Cuernavaca (Mexico)

    2011-10-15

    Experimental results of electron paramagnetic resonance spectra, X-ray diffraction, scanning electron microscopy and infrared spectroscopy demonstrate that the kinetic of the physical and chemical processes that takes place during prolonged intensive mechanical processing (MP, 03120min) of powder mixtures of 50%wt ZnO+50%wt MnO{sub 2} can be described as a three stage process. (1) 030min, particles destruction, formation of superficial defects, fast increment of sample average temperature (from 290 to {approx}600K) and annealing of defects with the lowest energy of activation E{sub ac}. (2) 30390min, further particle destruction, slow increment of sample average temperature (from {approx}600 to {approx}700K), formation and growth of a very disordered layer of {beta}-MnO{sub 2} around ZnO particles, dehydration of MnO{sub 2}, formation of solid solution of Mn{sup 2+} ions in ZnO, formation of nano-quasiamorphous states in the ZnO-MnO{sub 2} mixture and onset of the formation of the ZnMnO{sub 3} phase. (3) 3903120min, the sample average temperature remains constant ({approx}700K), the reaction is completed and the spinel ZnMnO{sub 3} phase with a unit cell a=8.431(1) A and space group Fd3-barm is the only phase present in the sample. No ferromagnetism at room temperature was detected in this study. - Highlights: > The kinetics during mechanical processing of ZnO-MnO{sub 2} samples is a three stage process. > First stage, reduction of crystallites size and accumulation of defects. > Second stage, nano-quasiamorphous states formation and onset of the ZnMnO{sub 3} phase. > Third stage, complete reaction to the spinel ZnMnO{sub 3} phase.

  1. Point defects and diffusion in alloys: correlation effects

    International Nuclear Information System (INIS)

    Barbe, Vincent

    2006-01-01

    Kinetic models in alloys aim at predicting the transport properties of a system starting from the microscopic jump frequencies of defects. Such properties are of prior importance in systems which stay out of equilibrium for a long time, as for example irradiated alloys in nuclear reactors. We hereby propose several developments of the recent self-consistent mean field (SCMF) kinetic theory, which deals particularly with the correlation effects due to the coupling of atomic and defect fluxes. They are taken into account through a non-equilibrium distribution function of the system, which is derived from the time evolution of small clusters (of two or more atoms or defects). We therefore introduce a set of 'dynamic' interactions called effective Hamiltonian. The SCMF theory is extended to treat high jump frequency ratios for the vacancy mechanism, as well as the transport through interstitial defects. We use in both cases an atomic model which accounts for the thermodynamic properties of the alloy, as e.g. the short-range order. Those models are eventually applied to predict the diffusion properties in two model alloys of nuclear interest: the concentrated Fe-Ni-Cr solid solution and the dilute Fe(P) alloy. We present adapted atomic models and compare our predictions to experimental data. (author)

  2. Temperature influence on the reaction kinetics of V(IV)/V(V) in methanesulfonic acid for all-vanadium redox flow battery

    International Nuclear Information System (INIS)

    Wang, Qiuhong; Daoud, Walid A.

    2016-01-01

    Highlights: • Diffusion coefficients and standard rate constants of V(IV) and V(V) in MSA at different temperatures are studied. • Carbon-based and metal electrodes are investigated under the same experimental condition at high temperature. • The influence of temperature on reaction kinetics is more significant on carbon-based electrode than metal electrode. • Gold electrode shows inefficient performance in MSA solution. - Abstract: In this study, methanesulfonic acid has been investigated as the supporting electrolyte for vanadium solutions due to the improvement of mass transfer rate and reaction kinetics. Here, we applied different temperatures (0–55 °C) for electrochemical experiments of 0.1 M vanadium ions in 1.0 M MSA electrolyte on gold, platinum and glassy carbon electrodes separately to study the temperature-related kinetics. Considering that electron transfer is the control path for the whole reduction potential window, the rotating disc electrode approach was utilized for the oxidation of V(IV) ions, while the reduction of V(V) ions was studied by cyclic voltammetry. The influence of temperature on charge-transfer resistance and mass transport for both V(IV) and V(V) solutions was studied by electrochemical impedance spectroscopy on glassy carbon electrode. The results showed that the diffusion coefficients in both redox reactions on all electrodes increased with temperature, and most were in the order of 10 −6 cm 2 s −1 . The positive influence of temperature was also observed on the standard rate constants for all conditions in this study, most significantly on the glassy carbon electrode. Comparison between glassy carbon electrode and metal electrodes indicates a promising potential of carbon-based material as electrode for redox flow battery.

  3. Reactions of the CN Radical with Benzene and Toluene: Product Detection and Low-Temperature Kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Trevitt, Adam J.; Goulay, Fabien; Taatjes, Craig A.; Osborn, David L.; Leone, Stephen R.

    2009-12-23

    Low temperature rate coefficients are measured for the CN + benzene and CN + toluene reactions using the pulsed Laval nozzle expansion technique coupled with laser-induced fluorescence detection. The CN + benzene reaction rate coefficient at 105, 165 and 295 K is found to be relatively constant over this temperature range, 3.9 - 4.9 x 10-10 cm3 molecule-1 s-1. These rapid kinetics, along with the observed negligible temperature dependence, are consistent with a barrierless reaction entrance channel and reaction efficiencies approaching unity. The CN + toluene reaction is measured to have a slower rate coefficient of 1.3 x 10-10 cm3 molecule-1 s-1 at 105 K. At room temperature, non-exponential decay profiles are observed for this reaction that may suggest significant back-dissociation of intermediate complexes. In separate experiments, the products of these reactions are probed at room temperature using synchrotron VUV photoionization mass spectrometry. For CN + benzene, cyanobenzene (C6H5CN) is the only product recorded with no detectable evidence for a C6H5 + HCN product channel. In the case of CN + toluene, cyanotoluene (NCC6H4CH3) constitutes the only detected product. It is not possible to differentiate among the ortho, meta and para isomers of cyanotoluene because of their similar ionization energies and the ~;; 40 meV photon energy resolution of the experiment. There is no significant detection of benzyl radicals (C6H5CH2) that would suggest a H-abstraction or a HCN elimination channel is prominent at these conditions. As both reactions are measured to be rapid at 105 K, appearing to have barrierless entrance channels, it follows that they will proceed efficiently at the temperatures of Saturn?s moon Titan (~;;100 K) and are also likely to proceed at the temperature of interstellar clouds (10-20 K).

  4. Full Kinetics from First Principles of the Chlorine Evolution Reaction over a RuO2 (110) Model Electrode.

    Science.gov (United States)

    Exner, Kai S; Anton, Josef; Jacob, Timo; Over, Herbert

    2016-06-20

    Current progress in modern electrocatalysis research is spurred by theory, frequently based on ab initio thermodynamics, where the stable reaction intermediates at the electrode surface are identified, while the actual energy barriers are ignored. This approach is popular in that a simple tool is available for searching for promising electrode materials. However, thermodynamics alone may be misleading to assess the catalytic activity of an electrochemical reaction as we exemplify with the chlorine evolution reaction (CER) over a RuO2 (110) model electrode. The full procedure is introduced, starting from the stable reaction intermediates, computing the energy barriers, and finally performing microkinetic simulations, all performed under the influence of the solvent and the electrode potential. Full kinetics from first-principles allows the rate-determining step in the CER to be identified and the experimentally observed change in the Tafel slope to be explained. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Lumping procedure for a kinetic model of catalytic naphtha reforming

    Directory of Open Access Journals (Sweden)

    H. M. Arani

    2009-12-01

    Full Text Available A lumping procedure is developed for obtaining kinetic and thermodynamic parameters of catalytic naphtha reforming. All kinetic and deactivation parameters are estimated from industrial data and thermodynamic parameters are calculated from derived mathematical expressions. The proposed model contains 17 lumps that include the C6 to C8+ hydrocarbon range and 15 reaction pathways. Hougen-Watson Langmuir-Hinshelwood type reaction rate expressions are used for kinetic simulation of catalytic reactions. The kinetic parameters are benchmarked with several sets of plant data and estimated by the SQP optimization method. After calculation of deactivation and kinetic parameters, plant data are compared with model predictions and only minor deviations between experimental and calculated data are generally observed.

  6. Insights into Sonogashira cross-coupling by high-throughput kinetics and descriptor modeling

    NARCIS (Netherlands)

    an der Heiden, M.R.; Plenio, H.; Immel, S.; Burello, E.; Rothenberg, G.; Hoefsloot, H.C.J.

    2008-01-01

    A method is presented for the high-throughput monitoring of reaction kinetics in homogeneous catalysis, running up to 25 coupling reactions in a single reaction vessel. This method is demonstrated and validated on the Sonogashira reaction, analyzing the kinetics for almost 500 coupling reactions.

  7. Thermogravimetric kinetic study of agricultural residue biomass pyrolysis based on combined kinetics.

    Science.gov (United States)

    Wang, Xun; Hu, Mian; Hu, Wanyong; Chen, Zhihua; Liu, Shiming; Hu, Zhiquan; Xiao, Bo

    2016-11-01

    Pyrolytic kinetic of an agricultural residue (AR) feedstock, a mixture of plants (cotton, wheat, rich, corn) stems, was investigated based on combined kinetics. The most suitable mechanism for AR one-step pyrolysis was f(α)=(1-α)(1.1816)α(-1.8428) with kinetic parameters of: apparent activation energy 221.7kJ/mol, pre-exponential factor 4.17E16s(-1). Pyrolysis of AR feedstock could not be described by one-step reaction attributes to heterogeneous features of pyrolysis processes. Combined kinetics three-parallel-reaction (CK-TPR) model fitted the pyrolysis experimental data very well. Reaction mechanisms for pseudo hemicelluloses, cellulose, lignin in CK-TPR model was f(α)=(1-α)(1.6244)α(-0.3371)[-ln(1-α)](-0.0515), f(α)=(1-α)(1.0597)α(-0.6909)[-ln(1-α)](0.9026) and f(α)=(1-α)(2.9577)α(-4.7719), respectively. Apparent activation energy of three pseudo components followed the order of Elignin(197.3kJ/mol)>Ecellulose(176.3kJ/mol)>Ehemicelluloses (151.1kJ/mol). Mechanism of hemicelluloses pyrolysis could be further expressed as f(α)=(1-α)(1.4). The pyrolytic mechanism of cellulose met the Nucleation well. However, mechanism of lignin pyrolysis was complex, which possibly was the combined effects of Nucleation, Diffusion, Geometrical contraction, and Power law. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Kinetics of the reaction between H{sup ·} and superheated water probed with muonium

    Energy Technology Data Exchange (ETDEWEB)

    Alcorn, Chris D. [Department of Chemistry and Biochemistry, Mount Allison University, Sackville, New Brunswick E4L 1G8 (Canada); Brodovitch, Jean-Claude [Department of Chemistry, Simon Fraser University, Burnaby, British Columbia V5A 1S6 (Canada); Percival, Paul W. [Department of Chemistry, Simon Fraser University, Burnaby, British Columbia V5A 1S6 (Canada); TRIUMF, 4004 Wesbrook Mall, Vancouver, British Columbia V6T 2A3 (Canada); Smith, Marisa [Department of Chemistry and Biochemistry, Mount Allison University, Sackville, New Brunswick E4L 1G8 (Canada); Ghandi, Khashayar, E-mail: kghandi@mta.ca [Department of Chemistry and Biochemistry, Mount Allison University, Sackville, New Brunswick E4L 1G8 (Canada)

    2014-05-19

    Highlights: • Rate constants for reactions of H with water resolve a controversy. • H reacts with superheated water via two channels. • The findings have important implications for the safety of some nuclear power reactors. - Abstract: Safe operation of supercritical water-cooled reactors requires knowledge of the kinetics of transient species formed by the radiolysis of water in the range 300–650 °C. Using muonium, it is possible to study aqueous H{sup ·} atom chemistry over this temperature range. An important reaction to study is that of the H{sup ·} atom with water itself, because it is a potential source of molecular H{sub 2}. The concentration of H{sub 2} is important to plant coolant chemistry, as H{sub 2} is currently added to suppress oxidative corrosion in CANDU reactors. The reaction of muonium with H{sub 2}O and D{sub 2}O was studied experimentally up to 450 °C, and also via quantum chemical computations to investigate possible isotope effects. Our results suggest that although the H{sup ·} atom abstraction from H{sub 2}O is important at temperatures above 300 °C, the electron-producing channel (H{sup ·} + H{sub 2}O ⇌ H{sub 3}O{sup +} + e{sub aq}{sup -}) is significant at temperatures up to 300 °C, and becomes the dominant reaction channel at lower temperatures.

  9. A molecular dynamics simulation study of irradiation induced defects in gold nanowire

    Science.gov (United States)

    Liu, Wenqiang; Chen, Piheng; Qiu, Ruizhi; Khan, Maaz; Liu, Jie; Hou, Mingdong; Duan, Jinglai

    2017-08-01

    Displacement cascade in gold nanowires was studied using molecular dynamics computer simulations. Primary knock-on atoms (PKAs) with different kinetic energies were initiated either at the surface or at the center of the nanowires. We found three kinds of defects that were induced by the cascade, including point defects, stacking faults and crater at the surface. The starting points of PKAs influence the number of residual point defects, and this consequently affect the boundary of anti-radiation window which was proposed by calculation of diffusion of point defects to the free surface of nanowires. Formation of stacking faults that expanded the whole cross-section of gold nanowires was observed when the PKA's kinetic energy was higher than 5 keV. Increasing the PKA's kinetic energy up to more than 10 keV may lead to the formation of crater at the surface of nanowires due to microexplosion of hot atoms. At this energy, PKAs started from the center of nanowires can also result in the creation of crater because length of cascade region is comparable to diameter of nanowires. Both the two factors, namely initial positions of PKAs as well as the craters induced by higher energy irradiation, would influence the ability of radiation resistance of metal nanowires.

  10. Kinetic mechanism of the decomposition of dimethyltin dichloride

    NARCIS (Netherlands)

    Mol, van A.M.B.; Croon, de M.H.J.M.; Spee, C.I.M.A.; Schouten, J.C.

    1999-01-01

    Results are reported of a study of the intrinsic kinetics of gas phase reactions. For this purpose a reactor system is designed in such a way that concentration and temperature variations throughout the reactor can be neglected enabling investigation of intrinsic reaction kinetics. The gas phase

  11. Kinetic analysis of overlapping multistep thermal decomposition comprising exothermic and endothermic processes: thermolysis of ammonium dinitramide.

    Science.gov (United States)

    Muravyev, Nikita V; Koga, Nobuyoshi; Meerov, Dmitry B; Pivkina, Alla N

    2017-01-25

    This study focused on kinetic modeling of a specific type of multistep heterogeneous reaction comprising exothermic and endothermic reaction steps, as exemplified by the practical kinetic analysis of the experimental kinetic curves for the thermal decomposition of molten ammonium dinitramide (ADN). It is known that the thermal decomposition of ADN occurs as a consecutive two step mass-loss process comprising the decomposition of ADN and subsequent evaporation/decomposition of in situ generated ammonium nitrate. These reaction steps provide exothermic and endothermic contributions, respectively, to the overall thermal effect. The overall reaction process was deconvoluted into two reaction steps using simultaneously recorded thermogravimetry and differential scanning calorimetry (TG-DSC) curves by considering the different physical meanings of the kinetic data derived from TG and DSC by P value analysis. The kinetic data thus separated into exothermic and endothermic reaction steps were kinetically characterized using kinetic computation methods including isoconversional method, combined kinetic analysis, and master plot method. The overall kinetic behavior was reproduced as the sum of the kinetic equations for each reaction step considering the contributions to the rate data derived from TG and DSC. During reproduction of the kinetic behavior, the kinetic parameters and contributions of each reaction step were optimized using kinetic deconvolution analysis. As a result, the thermal decomposition of ADN was successfully modeled as partially overlapping exothermic and endothermic reaction steps. The logic of the kinetic modeling was critically examined, and the practical usefulness of phenomenological modeling for the thermal decomposition of ADN was illustrated to demonstrate the validity of the methodology and its applicability to similar complex reaction processes.

  12. Kinetics of the Reactions of O((sup 3)P) and Cl((sup 2)P) with HBr and Br2

    Science.gov (United States)

    Nicovich, J. M.; Wine, P. H.

    1997-01-01

    A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of reactions (1)-(4) as a function of temperature. (1) O((sup 3)P) + Br2 yields BrO + Br((sup 2)P(sub 3/2)) at 255-350 K; (2) Cl((sup 2)P) + Br2 yields BrCl + Br((sup 2)P(sub 3/2)) at 298-401 K; (3) O((sup 3)P) + HBr yields OH + Br((sup 2)P(sub J)) at 250-402 K; (4) Cl((sup 2)P) + HBr yields HCl + Br((sup 2)P(sub J)) at 257-404 K. In all cases, the concentration of the excess reagent, i.e, HBr or Br2, was measured in situ in the slow flow system by UV-visible photometry. Heterogeneous dark reactions between XBr (X equals H or Br) and the photolytic precursors for Cl((sup 2)P) and O((sup 3)P) (Cl2 and O3, respectively) were avoided by injecting minimal amounts of precursor into the reaction mixture immediately upstream from the reaction zone. The following Arrhenius expressions summarize our results (errors are 2 sigma and represent precision only, units are cu cm/(molecule.s): k(sub 1) = (1.76 +/- 0.80) x 10(exp -11 exp[(40 +/- 100)/T]; k(sub 2) = (2.40 +/- 1.25) x 12(exp -10) exp[-(144 +/- 176)/T]; k(sub 3) = (5.11 +/- 2.82) x 10(exp -12) exp[-(1450 +/- 160)/T]; k(sub 4) = (2.25 +/- 0.56) x 10(exp -11) exp[-(400 +/- 80)/T]. The consistency (or lack thereof) of our results with those reported in previous kinetics and dynamics studies of reactions (1)-(4) is discussed.

  13. Di-interstitial defect in silicon revisited

    International Nuclear Information System (INIS)

    Londos, C. A.; Antonaras, G.; Chroneos, A.

    2013-01-01

    Infrared spectroscopy was used to study the defect spectrum of Cz-Si samples following fast neutron irradiation. We mainly focus on the band at 533 cm −1 , which disappears from the spectra at ∼170 °C, exhibiting similar thermal stability with the Si-P6 electron paramagnetic resonance (EPR) spectrum previously correlated with the di-interstitial defect. The suggested structural model of this defect comprises of two self-interstitial atoms located symmetrically around a lattice site Si atom. The band anneals out following a first-order kinetics with an activation energy of 0.88 ± 0.3 eV. This value does not deviate considerably from previously quoted experimental and theoretical values for the di-interstitial defect. The present results indicate that the 533 cm −1 IR band originates from the same structure as that of the Si-P6 EPR spectrum

  14. A Capacity Fading Model of Lithium-Ion Battery Cycle Life Based on the Kinetics of Side Reactions for Electric Vehicle Applications

    International Nuclear Information System (INIS)

    Gu, Weijun; Sun, Zechang; Wei, Xuezhe; Dai, Haifeng

    2014-01-01

    Highlights: • Describe the aging mechanism of lithium-ion battery with electrochemical kinetics. • Establish the fading rate equation based on Eyring Equation. • The established equation is applicable to any reaction order. • Integrate the internal kinetics with external degradation characteristics. - Abstract: Battery life prediction is one of the critical issues that restrict the development of electric vehicles. Among the typical battery life models, the mechanism model focusing on the internal physical or electrochemical processes has a stronger theoretical foundation and greater accuracy. The empirical formula, which relies on the simplified mechanism, has a concise model structure and more flexibility in vehicle applications. However, the internal aging mechanism rarely correlates with the external operating characteristics. Based on the summary of the capacity fading mechanism and the reasoning of the internal kinetics of side reactions during the aging process, a lifetime model of the lithium-ion battery is established in this paper. The solutions to the vital parameters based on the external accelerated life testing results are also presented. The testing sample is a manganese oxide lithium-ion battery of 8 Ah