WorldWideScience

Sample records for chemical kinetic mechanism

  1. 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.

  2. Chemical kinetic reaction mechanism for the combustion of propane

    Science.gov (United States)

    Jachimowski, C. J.

    1984-01-01

    A detailed chemical kinetic reaction mechanism for the combustion of propane is presented and discussed. The mechanism consists of 27 chemical species and 83 elementary chemical reactions. Ignition and combustion data as determined in shock tube studies were used to evaluate the mechanism. Numerical simulation of the shock tube experiments showed that the kinetic behavior predicted by the mechanism for stoichiometric mixtures is in good agrement with the experimental results over the entire temperature range examined (1150-2600K). Sensitivity and theoretical studies carried out using the mechanism revealed that hydrocarbon reactions which are involved in the formation of the HO2 radical and the H2O2 molecule are very important in the mechanism and that the observed nonlinear behavior of ignition delay time with decreasing temperature can be interpreted in terms of the increased importance of the HO2 and H2O2 reactions at the lower temperatures.

  3. Physical Chemistry Chemical Kinetics and Reaction Mechanism

    CERN Document Server

    Trimm, Harold H

    2011-01-01

    Physical chemistry covers diverse topics, from biochemistry to materials properties to the development of quantum computers. Physical chemistry applies physics and math to problems that interest chemists, biologists, and engineers. Physical chemists use theoretical constructs and mathematical computations to understand chemical properties and describe the behavior of molecular and condensed matter. Their work involves manipulations of data as well as materials. Physical chemistry entails extensive work with sophisticated instrumentation and equipment as well as state-of-the-art computers. This

  4. Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

    Energy Technology Data Exchange (ETDEWEB)

    Herbinet, O; Pitz, W J; Westbrook, C K

    2007-09-20

    A detailed chemical kinetic mechanism has been developed and used to study the oxidation of methyl decanoate, a surrogate for biodiesel fuels. This model has been built by following the rules established by Curran et al. for the oxidation of n-heptane and it includes all the reactions known to be pertinent to both low and high temperatures. Computed results have been compared with methyl decanoate experiments in an engine and oxidation of rapeseed oil methyl esters in a jet stirred reactor. An important feature of this mechanism is its ability to reproduce the early formation of carbon dioxide that is unique to biofuels and due to the presence of the ester group in the reactant. The model also predicts ignition delay times and OH profiles very close to observed values in shock tube experiments fueled by n-decane. These model capabilities indicate that large n-alkanes can be good surrogates for large methyl esters and biodiesel fuels to predict overall reactivity, but some kinetic details, including early CO{sub 2} production from biodiesel fuels, can be predicted only by a detailed kinetic mechanism for a true methyl ester fuel. The present methyl decanoate mechanism provides a realistic kinetic tool for simulation of biodiesel fuels.

  5. Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

    Energy Technology Data Exchange (ETDEWEB)

    Herbinet, O; Pitz, W J; Westbrook, C K

    2007-09-17

    A detailed chemical kinetic mechanism has been developed and used to study the oxidation of methyl decanoate, a surrogate for biodiesel fuels. This model has been built by following the rules established by Curran et al. for the oxidation of n-heptane and it includes all the reactions known to be pertinent to both low and high temperatures. Computed results have been compared with methyl decanoate experiments in an engine and oxidation of rapeseed oil methyl esters in a jet stirred reactor. An important feature of this mechanism is its ability to reproduce the early formation of carbon dioxide that is unique to biofuels and due to the presence of the ester group in the reactant. The model also predicts ignition delay times and OH profiles very close to observed values in shock tube experiments fueled by n-decane. These model capabilities indicate that large n-alkanes can be good surrogates for large methyl esters and biodiesel fuels to predict overall reactivity, but some kinetic details, including early CO2 production from biodiesel fuels, can be predicted only by a detailed kinetic mechanism for a true methyl ester fuel. The present methyl decanoate mechanism provides a realistic kinetic tool for simulation of biodiesel fuels.

  6. A multipurpose reduced chemical-kinetic mechanism for methanol combustion

    Science.gov (United States)

    Fernández-Tarrazo, Eduardo; Sánchez-Sanz, Mario; Sánchez, Antonio L.; Williams, Forman A.

    2016-07-01

    A multipurpose reduced chemical-kinetic mechanism for methanol combustion comprising 8 overall reactions and 11 reacting chemical species is presented. The development starts by investigating the minimum set of elementary reactions needed to describe methanol combustion with reasonable accuracy over a range of conditions of temperature, pressure, and composition of interest in combustion. Starting from a 27-step mechanism that has been previously tested and found to give accurate predictions of ignition processes for these conditions, it is determined that the addition of 11 elementary reactions taken from its basis (San Diego) mechanism extends the validity of the description to premixed-flame propagation, strain-induced extinction of non-premixed flames, and equilibrium composition and temperatures, giving results that compare favourably with experimental measurements and also with computations using the 247-step detailed San Diego mechanism involving 50 reactive species. Specifically, premixed-flame propagation velocities and extinction strain rates for non-premixed counterflow flames calculated with the 38-step mechanism show departures from experimental measurements and detailed-chemistry computations that are roughly on the order of 10%, comparable with expected experimental uncertainties. Similar accuracy is found in comparisons of autoignition times over the range considered, except at very high temperatures, under which conditions the computations tend to overpredict induction times for all of the chemistry descriptions tested. From this 38-step mechanism, the simplification is continued by introducing steady-state approximations for the intermediate species CH3, CH4, HCO, CH3O, CH2OH, and O, leading to an 8-step reduced mechanism that provides satisfactory accuracy for all conditions tested. The flame computations indicate that thermal diffusion has a negligible influence on methanol combustion in all cases considered and that a mixture-average species

  7. Planarization mechanism of alkaline copper CMP slurry based on chemical mechanical kinetics

    Institute of Scientific and Technical Information of China (English)

    Wang Shengli; Yin Kangda; Li Xiang; Yue Hongwei; Liu Yunling

    2013-01-01

    The planarization mechanism of alkaline copper slurry is studied in the chemical mechanical polishing (CMP) process from the perspective of chemical mechanical kinetics.Different from the international dominant acidic copper slurry,the copper slurry used in this research adopted the way of alkaline technology based on complexation.According to the passivation property of copper in alkaline conditions,the protection of copper film at the concave position on a copper pattern wafer surface can be achieved without the corrosion inhibitors such as benzotriazole (BTA),by which the problems caused by BTA can be avoided.Through the experiments and theories research,the chemical mechanical kinetics theory of copper removal in alkaline CMP conditions was proposed.Based on the chemical mechanical kinetics theory,the planarization mechanism of alkaline copper slurry was established.In alkaline CMP conditions,the complexation reaction between chelating agent and copper ions needs to break through the reaction barrier.The kinetic energy at the concave position should be lower than the complexation reaction barrier,which is the key to achieve planarization.

  8. The Mechanism of Surface Chemical Kinetics of Dissolution of Minerals

    Institute of Scientific and Technical Information of China (English)

    谭凯旋; 张哲儒; 等

    1996-01-01

    This paper deals with the mechanism of dissolution reaction kinetics of minerals in aqueous solution based on the theory of surface chemistry.Surface chemical catalysis would lead to an obvous decrease in active energy of dissolution reaction of minerals.The dissolution rate of minerals is controlled by suface adsorption,surface exchange reaction and desorption,depending on pH of the solution and is directly proportional to δHn0+,When controlled by surface adsorption,i.e.,nθ=1,the dissolution rate will decrease with increasing pH;when controlled by surface exchane reaction,i.e.,nθ=0,the dissolution rate is independent of pH;when controlled by desorption,nθis a positive decimal between 0 and 1 in acidic solution and a negative decimal between-1 and 0 in alkaline solution.Dissolution of many minerals is controlled by surface adsorption and/or surface exchange reactions under acid conditions and by desorption under alkaline conditions.

  9. Development and Validation of Chemical Kinetic Mechanism Reduction Scheme for Large-Scale Mechanisms

    DEFF Research Database (Denmark)

    Poon, Hiew Mun; Ng, Hoon Kiat; Gan, Suyin;

    2014-01-01

    This work is an extension to a previously reported work on chemical kinetic mechanism reduction scheme for large-scale mechanisms. Here, Perfectly Stirred Reactor (PSR) was added as a criterion of data source for mechanism reduction instead of using only auto-ignition condition. As a result......, a reduced n-hexadecane mechanism with 79 species for diesel fuel surrogate was successfully derived from the detailed mechanism. Following that, the reduced n-hexadecane mechanism was validated under auto-ignition and PSR conditions using zero-dimensional (0-D) closed homogeneous batch reactor in CHEMKIN...

  10. 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

  11. Chemical and Biological Kinetics

    Science.gov (United States)

    Emanuel', N. M.

    1981-10-01

    Examples of the application of the methods and ideas of chemical kinetics in various branches of chemistry and biology are considered and the results of studies on the kinetics and mechanisms of autoxidation and inhibited and catalysed oxidation of organic substances in the liquid phase are surveyed. Problems of the kinetics of the ageing of polymers and the principles of their stabilisation are discussed and certain trends in biological kinetics (kinetics of tumour growth, kinetic criteria of the effectiveness of chemotherapy, problems of gerontology, etc.) are considered. The bibliography includes 281 references.

  12. Mechanistic, kinetic, and processing aspects of tungsten chemical mechanical polishing

    Science.gov (United States)

    Stein, David

    This dissertation presents an investigation into tungsten chemical mechanical polishing (CMP). CMP is the industrially predominant unit operation that removes excess tungsten after non-selective chemical vapor deposition (CVD) during sub-micron integrated circuit (IC) manufacture. This work explores the CMP process from process engineering and fundamental mechanistic perspectives. The process engineering study optimized an existing CMP process to address issues of polish pad and wafer carrier life. Polish rates, post-CMP metrology of patterned wafers, electrical test data, and synergy with a thermal endpoint technique were used to determine the optimal process. The oxidation rate of tungsten during CMP is significantly lower than the removal rate under identical conditions. Tungsten polished without inhibition during cathodic potentiostatic control. Hertzian indenter model calculations preclude colloids of the size used in tungsten CMP slurries from indenting the tungsten surface. AFM surface topography maps and TEM images of post-CMP tungsten do not show evidence of plow marks or intergranular fracture. Polish rate is dependent on potassium iodate concentration; process temperature is not. The colloid species significantly affects the polish rate and process temperature. Process temperature is not a predictor of polish rate. A process energy balance indicates that the process temperature is predominantly due to shaft work, and that any heat of reaction evolved during the CMP process is negligible. Friction and adhesion between alumina and tungsten were studied using modified AFM techniques. Friction was constant with potassium iodate concentration, but varied with applied pressure. This corroborates the results from the energy balance. Adhesion between the alumina and the tungsten was proportional to the potassium iodate concentration. A heuristic mechanism, which captures the relationship between polish rate, pressure, velocity, and slurry chemistry, is presented

  13. Chemical kinetic mechanism for the oxidation of paraffinic hydrocarbons needed for primary reference fuels

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C.K.; Pitz, W.J.

    1993-03-01

    A detailed chemical kinetic reaction mechanism is described which simulates the oxidation of the primary reference fuels n-heptane and iso-octane. The high temperature subset of these mechanisms is identified, and the extensions to deal with low temperature conditions are also explained. The algorithms used to assign reaction rates to elementary steps in the reaction mechanism are described, and the means of identifying the different chemical species and the relevant reactions are outlined. Finally, we show how interested kinetic modeling researchers can obtain copies of this reaction mechanism.

  14. 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

  15. Reduced chemical kinetic mechanisms for NOx emission prediction in biomass combustion

    DEFF Research Database (Denmark)

    Houshfar, Ehsan; Skreiberg, Øyvind; Glarborg, Peter;

    2012-01-01

    Because of the complex composition of biomass, the chemical mechanism contains many different species and therefore a large number of reactions. Although biomass gas‐phase combustion is fairly well researched and understood, the proposed mechanisms are still complex and need very long computational...... reactions and chemical species, that is, 35 species and 198 reactions, corresponding to 72% reduction in the number of reactions and, therefore, improving the computational time considerably. Yet, the model based on the reduced mechanism predicts correctly concentrations of NOx and CO that are essentially...... parameters on NOx emission. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 219–231, 2012...

  16. Evaluation and Development of Chemical Kinetic Mechanism Reduction Scheme for Biodiesel and Diesel Fuel Surrogates

    DEFF Research Database (Denmark)

    Poon, Hiew Mun; Ng, Hoon Kiat; Gan, Suyin;

    2013-01-01

    The aim of this study is to evaluate the existing chemical kinetic mechanism reduction techniques. From here, an appropriate reduction scheme was developed to create compact yet comprehensive surrogate models for both diesel and biodiesel fuels for diesel engine applications. The reduction......-dimensional computational fluid dynamics (CFD) study. A new reduction scheme was therefore formulated. A 68-species mechanism for biodiesel surrogate and a 49-species mechanism for diesel surrogate were successfully derived from the respective detailed mechanisms. An overall 97% reduction in species number......-hexadecane mechanism is expected to be a better representative of surrogate component for various transportation fuels such as biodiesel. Additionally, it can be applied to predict the reactivity of other n-alkane or interchange with one another for kinetic and CFD simulations....

  17. Detailed chemical kinetic mechanism for the oxidation of biodiesel fuels blend surrogate.

    Energy Technology Data Exchange (ETDEWEB)

    Herbinet, O; Pitz, W J; Westbrook, C K

    2009-07-21

    Detailed chemical kinetic mechanisms were developed and used to study the oxidation of two large unsaturated esters: methyl-5-decenoate and methyl-9-decenoate. These models were built from a previous methyl decanoate mechanism and were compared with rapeseed oil methyl esters oxidation experiments in a jet stirred reactor. A comparative study of the reactivity of these three oxygenated compounds was performed and the differences in the distribution of the products of the reaction were highlighted showing the influence of the presence and the position of a double bond in the chain. Blend surrogates, containing methyl decanoate, methyl-5-decenoate, methyl-9-decenoate and n-alkanes, were tested against rapeseed oil methyl esters and methyl palmitate/n-decane experiments. These surrogate models are realistic kinetic tools allowing the study of the combustion of biodiesel fuels in diesel and homogeneous charge compression ignition engines.

  18. Integration of large chemical kinetic mechanisms via exponential methods with Krylov approximations to Jacobian matrix functions

    KAUST Repository

    Bisetti, Fabrizio

    2012-06-01

    Recent trends in hydrocarbon fuel research indicate that the number of species and reactions in chemical kinetic mechanisms is rapidly increasing in an effort to provide predictive capabilities for fuels of practical interest. In order to cope with the computational cost associated with the time integration of stiff, large chemical systems, a novel approach is proposed. The approach combines an exponential integrator and Krylov subspace approximations to the exponential function of the Jacobian matrix. The components of the approach are described in detail and applied to the ignition of stoichiometric methane-air and iso-octane-air mixtures, here described by two widely adopted chemical kinetic mechanisms. The approach is found to be robust even at relatively large time steps and the global error displays a nominal third-order convergence. The performance of the approach is improved by utilising an adaptive algorithm for the selection of the Krylov subspace size, which guarantees an approximation to the matrix exponential within user-defined error tolerance. The Krylov projection of the Jacobian matrix onto a low-dimensional space is interpreted as a local model reduction with a well-defined error control strategy. Finally, the performance of the approach is discussed with regard to the optimal selection of the parameters governing the accuracy of its individual components. © 2012 Copyright Taylor and Francis Group, LLC.

  19. Chemical kinetics modeling

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C.K.; Pitz, W.J. [Lawrence Livermore National Laboratory, CA (United States)

    1993-12-01

    This project emphasizes numerical modeling of chemical kinetics of combustion, including applications in both practical combustion systems and in controlled laboratory experiments. Elementary reaction rate parameters are combined into mechanisms which then describe the overall reaction of the fuels being studied. Detailed sensitivity analyses are used to identify those reaction rates and product species distributions to which the results are most sensitive and therefore warrant the greatest attention from other experimental and theoretical research programs. Experimental data from a variety of environments are combined together to validate the reaction mechanisms, including results from laminar flames, shock tubes, flow systems, detonations, and even internal combustion engines.

  20. Chemical Kinetics on Extrasolar Planets

    CERN Document Server

    Moses, Julianne I

    2013-01-01

    Chemical kinetics plays an important role in controlling the atmospheric composition of all planetary atmospheres, including those of extrasolar planets. For the hottest exoplanets, the composition can closely follow thermochemical-equilibrium predictions, at least in the visible and infrared photosphere at dayside (eclipse) conditions. However, for atmospheric temperatures < ~2000 K, and in the uppermost atmosphere at any temperature, chemical kinetics matters. The two key mechanisms by which kinetic processes drive an exoplanet atmosphere out of equilibrium are photochemistry and transport-induced quenching. We review these disequilibrium processes in detail, discuss observational consequences, and examine some of the current evidence for kinetic processes on extrasolar planets.

  1. An optimized chemical kinetic mechanism for HCCI combustion of PRFs using multi-zone model and genetic algorithm

    International Nuclear Information System (INIS)

    Highlights: • A new chemical kinetic mechanism for PRFs HCCI combustion is developed. • New mechanism optimization is performed using genetic algorithm and multi-zone model. • Engine-related combustion and performance parameters are predicted accurately. • Engine unburned HC and CO emissions are predicted by the model properly. - Abstract: Development of comprehensive chemical kinetic mechanisms is required for HCCI combustion and emissions prediction to be used in engine development. The main purpose of this study is development of a new chemical kinetic mechanism for primary reference fuels (PRFs) HCCI combustion, which can be applied to combustion models to predict in-cylinder pressure and exhaust CO and UHC emissions, accurately. Hence, a multi-zone model is developed for HCCI engine simulation. Two semi-detailed chemical kinetic mechanisms those are suitable for premixed combustion are used for n-heptane and iso-octane HCCI combustion simulation. The iso-octane mechanism contains 84 species and 484 reactions and the n-heptane mechanism contains 57 species and 296 reactions. A simple interaction between iso-octane and n-heptane is considered in new mechanism. The multi-zone model is validated using experimental data for pure n-heptane and iso-octane. A new mechanism is prepared by combination of these two mechanisms for n-heptane and iso-octane blended fuel, which includes 101 species and 594 reactions. New mechanism optimization is performed using genetic algorithm and multi-zone model. Mechanism contains low temperature heat release region, which decreases with increasing octane number. The results showed that the optimized chemical kinetic mechanism is capable of predicting engine-related combustion and performance parameters. Also after implementing the optimized mechanism, engine unburned HC and CO emissions predicted by the model are in good agreement with the corresponding experimental data

  2. 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

  3. Chemical Kinetics Database

    Science.gov (United States)

    SRD 17 NIST Chemical Kinetics Database (Web, free access)   The NIST Chemical Kinetics Database includes essentially all reported kinetics results for thermal gas-phase chemical reactions. The database is designed to be searched for kinetics data based on the specific reactants involved, for reactions resulting in specified products, for all the reactions of a particular species, or for various combinations of these. In addition, the bibliography can be searched by author name or combination of names. The database contains in excess of 38,000 separate reaction records for over 11,700 distinct reactant pairs. These data have been abstracted from over 12,000 papers with literature coverage through early 2000.

  4. Modeling chemical kinetics graphically

    NARCIS (Netherlands)

    A. Heck

    2012-01-01

    In literature on chemistry education it has often been suggested that students, at high school level and beyond, can benefit in their studies of chemical kinetics from computer supported activities. Use of system dynamics modeling software is one of the suggested quantitative approaches that could h

  5. Surftherm: A program to analyze thermochemical and kinetic data in gas-phase and surface chemical reaction mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Coltrin, M.E.; Moffat, H.K.

    1994-06-01

    This report documents the Surftherm program that analyzes transport coefficient, thermochemical- and kinetic rate information in complex gas-phase and surface chemical reaction mechanisms. The program is designed for use with the Chemkin (gas-phase chemistry) and Surface Chemkin (heterogeneous chemistry) programs. It was developed as a ``chemist`s companion`` in using the Chemkin packages with complex chemical reaction mechanisms. It presents in tabular form detailed information about the temperature and pressure dependence of chemical reaction rate constants and their reverse rate constants, reaction equilibrium constants, reaction thermochemistry, chemical species thermochemistry and transport properties. This report serves as a user`s manual for use of the program, explaining the required input and the output.

  6. Detailed Chemical Kinetic Reaction Mechanisms for Primary Reference Fuels for Diesel Cetane Number and Spark-Ignition Octane Number

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C K; Pitz, W J; Mehl, M; Curran, H J

    2010-03-03

    For the first time, a detailed chemical kinetic reaction mechanism is developed for primary reference fuel mixtures of n-hexadecane and 2,2,4,4,6,8,8-heptamethyl nonane for diesel cetane ratings. The mechanisms are constructed using existing rules for reaction pathways and rate expressions developed previously for the primary reference fuels for gasoline octane ratings, n-heptane and iso-octane. These reaction mechanisms are validated by comparisons between computed and experimental results for shock tube ignition and for oxidation under jet-stirred reactor conditions. The combined kinetic reaction mechanism contains the submechanisms for the primary reference fuels for diesel cetane ratings and submechanisms for the primary reference fuels for gasoline octane ratings, all in one integrated large kinetic reaction mechanism. Representative applications of this mechanism to two test problems are presented, one describing fuel/air autoignition variations with changes in fuel cetane numbers, and the other describing fuel combustion in a jet-stirred reactor environment with the fuel varying from pure 2,2,4,4,6,8,8-heptamethyl nonane (Cetane number of 15) to pure n-hexadecane (Cetane number of 100). The final reaction mechanism for the primary reference fuels for diesel fuel and gasoline is available on the web.

  7. Development and validation of a generic reduced chemical kinetic mechanism for CFD spray combustion modelling of biodiesel fuels

    DEFF Research Database (Denmark)

    Cheng, Xinwei; Ng, Hoon Kiat; Ho, Jee Hou;

    2015-01-01

    In this reported work, a generic reduced biodiesel chemical kinetic mechanism, with components of methyl decanoate (C11H22O2, MD), methyl-9-decenoate (C11H20O2, MD9D) and n-heptane (C7H16) was built to represent the methyl esters of coconut, palm, rapeseed and soybean. The reduced biodiesel...... deviation of 1 order in the mole fraction values. Meanwhile, satisfactory agreement was achieved when the predictions of reduced mechanism were compared against the measured ID periods of MD auto-ignition event in shock tube conditions and key species profiles of RME oxidation in jet stirred reactor (JSR...

  8. New Patterns in Steady-State Chemical Kinetics: Intersections, Coincidences, Map of Events (Two-Step Mechanism

    Directory of Open Access Journals (Sweden)

    Daniel Branco Pinto

    2015-10-01

    Full Text Available New patterns of steady-state chemical kinetics for continuously stirred-tank reactors (CSTR have been found, i.e., intersections, maxima and coincidences, for two-step mechanism A↔B→C. There were found elegant analytical relationships for characteristics of these patterns (space times, values of concentrations and rates allowing kinetic parameters to be easily determined. It was demonstrated that for the pair of species involved into the irreversible reaction (B and C, the space time of their corresponding concentration dependence intersection is invariant and does not depend on the initial conditions of the system. Maps of patterns are presented for visualization of their combinations and ranking in space time, and values of concentration and rates.

  9. Entropy production in mesoscopic stochastic thermodynamics: nonequilibrium kinetic cycles driven by chemical potentials, temperatures, and mechanical forces

    Science.gov (United States)

    Qian, Hong; Kjelstrup, Signe; Kolomeisky, Anatoly B.; Bedeaux, Dick

    2016-04-01

    Nonequilibrium thermodynamics (NET) investigates processes in systems out of global equilibrium. On a mesoscopic level, it provides a statistical dynamic description of various complex phenomena such as chemical reactions, ion transport, diffusion, thermochemical, thermomechanical and mechanochemical fluxes. In the present review, we introduce a mesoscopic stochastic formulation of NET by analyzing entropy production in several simple examples. The fundamental role of nonequilibrium steady-state cycle kinetics is emphasized. The statistical mechanics of Onsager’s reciprocal relations in this context is elucidated. Chemomechanical, thermomechanical, and enzyme-catalyzed thermochemical energy transduction processes are discussed. It is argued that mesoscopic stochastic NET in phase space provides a rigorous mathematical basis of fundamental concepts needed for understanding complex processes in chemistry, physics and biology. This theory is also relevant for nanoscale technological advances.

  10. Entropy production in mesoscopic stochastic thermodynamics: nonequilibrium kinetic cycles driven by chemical potentials, temperatures, and mechanical forces

    International Nuclear Information System (INIS)

    Nonequilibrium thermodynamics (NET) investigates processes in systems out of global equilibrium. On a mesoscopic level, it provides a statistical dynamic description of various complex phenomena such as chemical reactions, ion transport, diffusion, thermochemical, thermomechanical and mechanochemical fluxes. In the present review, we introduce a mesoscopic stochastic formulation of NET by analyzing entropy production in several simple examples. The fundamental role of nonequilibrium steady-state cycle kinetics is emphasized. The statistical mechanics of Onsager’s reciprocal relations in this context is elucidated. Chemomechanical, thermomechanical, and enzyme-catalyzed thermochemical energy transduction processes are discussed. It is argued that mesoscopic stochastic NET in phase space provides a rigorous mathematical basis of fundamental concepts needed for understanding complex processes in chemistry, physics and biology. This theory is also relevant for nanoscale technological advances. (topical review)

  11. Computer Simulation in Chemical Kinetics

    Science.gov (United States)

    Anderson, Jay Martin

    1976-01-01

    Discusses the use of the System Dynamics technique in simulating a chemical reaction for kinetic analysis. Also discusses the use of simulation modelling in biology, ecology, and the social sciences, where experimentation may be impractical or impossible. (MLH)

  12. 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.

  13. Development of a Procedure to Apply Detailed Chemical Kinetic Mechanisms to CFD Simulations as Post Processing

    DEFF Research Database (Denmark)

    Skjøth-Rasmussen, Martin Skov; Glarborg, Peter; Jensen, Anker;

    2003-01-01

    mechanism. It involves post-processing of data extracted from computational fluid dynamics simulations. Application of this approach successfully describes combustion chemistry in a standard swirl burner, the so-called Harwell furnace. Nevertheless, it needs validation against more complex combustion models...

  14. 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

  15. 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

  16. Chemical kinetics and combustion modeling

    Energy Technology Data Exchange (ETDEWEB)

    Miller, J.A. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    The goal of this program is to gain qualitative insight into how pollutants are formed in combustion systems and to develop quantitative mathematical models to predict their formation rates. The approach is an integrated one, combining low-pressure flame experiments, chemical kinetics modeling, theory, and kinetics experiments to gain as clear a picture as possible of the process in question. These efforts are focused on problems involved with the nitrogen chemistry of combustion systems and on the formation of soot and PAH in flames.

  17. Numerical studies of spray combustion processes of palm oil biodiesel and diesel fuels using reduced chemical kinetic mechanisms

    KAUST Repository

    Kuti, Olawole

    2014-04-01

    Spray combustion processes of palm oil biodiesel (PO) and conventional diesel fuels were simulated using the CONVERGE CFD code. Thermochemical and reaction kinetic data (115 species and 460 reactions) by Luo et al. (2012) and Lu et al. (2009) (68 species and 283 reactions) were implemented in the CONVERGE CFD to simulate the spray and combustion processes of the two fuels. Tetradecane (C14H30) and n- heptane (C7H 16) were used as surrogates for diesel. For the palm biodiesel, the mixture of methyl decanoate (C11H20O2), methyl-9-decenoate (C11H19O2) and n-heptane was used as surrogate. The palm biodiesel surrogates were combined in proportions based on the previous GC-MS results for the five major biodiesel components namely methyl palmitate, methyl stearate, methyl oleate, methyl linoleate and methyl linolenate. The Favre-Averaged Navier Stokes based simulation using the renormalization group (RNG) k-ε turbulent model was implemented in the numerical calculations of the spray formation processes while the SAGE chemical kinetic solver is used for the detailed kinetic modeling. The SAGE chemical kinetic solver is directly coupled with the gas phase calculations by renormalization group (RNG) k-ε turbulent model using a well-stirred reactor model. Validations of the spray liquid length, ignition delay and flame lift-off length data were performed against previous experimental results. The simulated liquid length, ignition delay and flame lift-off length were validated at an ambient density of 15kg/m3, and injection pressure conditions of 100, 200 and 300 MPa were utilized. The predicted liquid length, ignition delay and flame lift-off length agree with the trends obtained in the experimental data at all injection conditions. Copyright © 2014 SAE International.

  18. Microreactor for fast chemical kinetics

    CERN Document Server

    Baroud, C N; Menetrier, L; Tabeling, P; Baroud, Charles N.; Okkels, Fridolin; Menetrier, Laure; Tabeling, Patrick

    2003-01-01

    The chemical reaction process in a T-shaped microchannel is studied experimentally through the reaction of Ca++ with a fluorescent tracer, Calcium-green. For thin channels (10 um), diffusion of species is found to behave in a way independent of the thickness direction. In such a situation, simulations of a two-dimensional reaction-diffusion model agree remarkably well with the experimental measurements. The comparison of experiments and simulations is used to measure the chemical kinetic constant, which we find to be k=3.2 x 10^5 dm^3/(mol s). Applications of the analysis to faster reactions and to micro-titration are also discussed.

  19. Thermogravimetric Analysis of Modified Hematite by Methane (CH{sub 4}) for Chemical-Looping Combustion: A Global Kinetics Mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Monazam, Esmail R; Breault, Ronald W; Siriwardane, Ranjani; Miller, Duane D

    2013-10-01

    Iron oxide (Fe{sub 2}O{sub 3}) or in its natural form (hematite) is a potential material to capture CO{sub 2} through the chemical-looping combustion (CLC) process. It is known that magnesium (Mg) is an effective methyl cleaving catalyst and as such it has been combined with hematite to assess any possible enhancement to the kinetic rate for the reduction of Fe{sub 2}O{sub 3} with methane. Therefore, in order to evaluate its effectiveness as a hematite additive, the behaviors of Mg-modified hematite samples (hematite –5% Mg(OH){sub 2}) have been analyzed with regard to assessing any enhancement to the kinetic rate process. The Mg-modified hematite was prepared by hydrothermal synthesis. The reactivity experiments were conducted in a thermogravimetric analyzer (TGA) using continuous stream of CH{sub 4} (5, 10, and 20%) at temperatures ranging from 700 to 825 {degrees}C over ten reduction cycles. The mass spectroscopy analysis of product gas indicated the presence of CO{sub 2}, H{sub 2}O, H{sub 2} and CO in the gaseous product. The kinetic data at reduction step obtained by isothermal experiments could be well fitted by two parallel rate equations. The modified hematite samples showed higher reactivity as compared to unmodified hematite samples during reduction at all investigated temperatures.

  20. Detailed Chemical Kinetic Modeling of Cyclohexane Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Silke, E J; Pitz, W J; Westbrook, C K; Ribaucour, M

    2006-11-10

    A detailed chemical kinetic mechanism has been developed and used to study the oxidation of cyclohexane at both low and high temperatures. Reaction rate constant rules are developed for the low temperature combustion of cyclohexane. These rules can be used for in chemical kinetic mechanisms for other cycloalkanes. Since cyclohexane produces only one type of cyclohexyl radical, much of the low temperature chemistry of cyclohexane is described in terms of one potential energy diagram showing the reaction of cyclohexyl radical + O{sub 2} through five, six and seven membered ring transition states. The direct elimination of cyclohexene and HO{sub 2} from RO{sub 2} is included in the treatment using a modified rate constant of Cavallotti et al. Published and unpublished data from the Lille rapid compression machine, as well as jet-stirred reactor data are used to validate the mechanism. The effect of heat loss is included in the simulations, an improvement on previous studies on cyclohexane. Calculations indicated that the production of 1,2-epoxycyclohexane observed in the experiments can not be simulated based on the current understanding of low temperature chemistry. Possible 'alternative' H-atom isomerizations leading to different products from the parent O{sub 2}QOOH radical were included in the low temperature chemical kinetic mechanism and were found to play a significant role.

  1. Quantum logics and chemical kinetics

    Science.gov (United States)

    Ivanov, C. I.

    1981-06-01

    A statistical theory of chemical kinetics is presented based on the quantum logical concept of chemical observables. The apparatus of Boolean algebra B is applied for the construction of appropriate composition polynomials referring to any stipulated arrangement of the atomic constituents. A physically motivated probability measure μ( F) is introduced on the field B of chemical observables, which considers the occurrence of the yes response of a given F ɛ B. The equations for the time evolution of the species density operators and the master equations for the corresponding number densities are derived. The general treatment is applied to a superposition of elementary substitution reactions (AB) α + C ⇄ (AC) β + B. The expressions for the reaction rate coefficients are established.

  2. A complex chemical kinetic mechanism for the oxidation of gasoline surrogate fuels: n heptane, iso octane and toluene - Mechanism development and validation

    CERN Document Server

    Da Cruz, A Pires; Anderlohr, Jörg; Bounaceur, Roda; Battin-Leclerc, Frédérique

    2009-01-01

    The development and validation against experimental results of a new gasoline surrogate complex kinetic mechanism is presented in this paper. The surrogate fuel is a ternary mixture of n heptane, iso octane and toluene. The full three components mechanism is based on existing n heptane/iso octane (gasoline PRF) and toluene mechanisms which were modified and coupled for the purpose of this work. Mechanism results are compared against available experimental data from the literature. Simulations with the PRF plus toluene mechanism show that its behavior is in agreement with experimental results for most of the tested settings. These include a wide variety of thermodynamic conditions and fuel proportions in experimental configurations such as HCCI engine experiments, rapid compression machines, a shock tube and a jet stirred reactor.

  3. Decomposition Mechanisms and Kinetics of Novel Energetic Molecules BNFF-1 and ANFF-1: Quantum-Chemical Modeling

    Directory of Open Access Journals (Sweden)

    Maija M. Kuklja

    2013-07-01

    Full Text Available Decomposition mechanisms, activation barriers, Arrhenius parameters, and reaction kinetics of the novel explosive compounds, 3,4-bis(4-nitro-1,2,5-oxadiazol-3-yl-1,2,5-oxadiazole (BNFF-1, and 3-(4-amino-1,2,5-oxadiazol-3-yl-4-(4-nitro-1,2,5-oxadiazol-3-yl-1,2,5-oxadiazole (ANFF-1 were explored by means of density functional theory with a range of functionals combined with variational transition state theory. BNFF-1 and ANFF-1 were recently suggested to be good candidates for insensitive high energy density materials. Our modeling reveals that the decomposition initiation in both BNFF-1 and ANFF-1 molecules is triggered by ring cleavage reactions while the further process is defined by a competition between two major pathways, the fast C-NO2 homolysis and slow nitro-nitrite isomerization releasing NO. We discuss insights on design of new energetic materials with targeted properties gained from our modeling.

  4. Enhancing Thai Students' Learning of Chemical Kinetics

    Science.gov (United States)

    Chairam, Sanoe; Somsook, Ekasith; Coll, Richard K.

    2009-01-01

    Chemical kinetics is an extremely important concept for introductory chemistry courses. The literature suggests that instruction in chemical kinetics is often teacher-dominated at both the secondary school and tertiary levels, and this is the case in Thailand--the educational context for this inquiry. The work reported here seeks to shift students…

  5. Chemical Kinetic Modeling of Biofuel Combustion

    Science.gov (United States)

    Sarathy, Subram Maniam

    Bioalcohols, such as bioethanol and biobutanol, are suitable replacements for gasoline, while biodiesel can replace petroleum diesel. Improving biofuel engine performance requires understanding its fundamental combustion properties and the pathways of combustion. This study's contribution is experimentally validated chemical kinetic combustion mechanisms for biobutanol and biodiesel. Fundamental combustion data and chemical kinetic mechanisms are presented and discussed to improve our understanding of biofuel combustion. The net environmental impact of biobutanol (i.e., n-butanol) has not been studied extensively, so this study first assesses the sustainability of n-butanol derived from corn. The results indicate that technical advances in fuel production are required before commercializing biobutanol. The primary contribution of this research is new experimental data and a novel chemical kinetic mechanism for n-butanol combustion. The results indicate that under the given experimental conditions, n-butanol is consumed primarily via abstraction of hydrogen atoms to produce fuel radical molecules, which subsequently decompose to smaller hydrocarbon and oxygenated species. The hydroxyl moiety in n-butanol results in the direct production of the oxygenated species such as butanal, acetaldehyde, and formaldehyde. The formation of these compounds sequesters carbon from forming soot precursors, but they may introduce other adverse environmental and health effects. Biodiesel is a mixture of long chain fatty acid methyl esters derived from fats and oils. This research study presents high quality experimental data for one large fatty acid methyl ester, methyl decanoate, and models its combustion using an improved skeletal mechanism. The results indicate that methyl decanoate is consumed via abstraction of hydrogen atoms to produce fuel radicals, which ultimately lead to the production of alkenes. The ester moiety in methyl decanoate leads to the formation of low molecular

  6. Investigating the chemical mechanisms of the functionalization and fragmentation of hydrocarbons in the heterogeneous oxidation by OH using a stochastic kinetics model

    Science.gov (United States)

    Wiegel, A. A.; Wilson, K. R.; Hinsberg, B.; Houle, F. A.

    2014-12-01

    While the heterogeneous oxidation of atmospheric organic aerosols influences their effects on climate, air quality, and visibility, a more detailed understanding of the chemical mechanisms in heterogeneous oxidation is crucial for improving models of their chemical evolution in the atmosphere. Previous experimental work in our lab has shown two general reaction pathways for organic aerosol upon oxidation: functionalization, which adds additional oxygen functional groups to the carbon skeleton, and fragmentation, which leads to C-C bond scission and lower molecular weight oxidized products. Furthermore, these pathways were also found to be dependent on molecular structure, with more branched or oxidized hydrocarbons undergoing more fragmentation than less branched or oxidized hydrocarbons. However, while the mechanisms of hydrocarbon oxidation have been studied extensively in the gas phase, to what extent the gas phase mechanisms of hydrocarbon oxidation can be reliably applied to heterogeneous or bulk oxidation in aerosol remains unclear. To investigate the role of the condensed phase and molecular structure in the mechanism of heterogeneous organic aerosol oxidation, stochastic kinetics models are developed and compared to measurements of the products in the oxidation of hydrocarbons. Within the aerosol bulk, condensed phase rate coefficients and product branching ratios for peroxy reactions lead to different product distributions than those expected from gas phase peroxy reactions due to the presence of the liquid radical cage at the reaction site. As a result, tertiary alcohols and ketones were found to be the predominate products in the oxidation of squalane as observed in experiments. As the aerosol becomes further oxidized, β-scission of alkoxy radicals with neighboring functional groups is the primary fragmentation pathway leading to lower volatility products. In conjunction with this fragmentation mechanism, elimination of CO2 from acyloxy radicals was

  7. Molecular Energy Relations From Chemical Kinetics

    OpenAIRE

    Finkel, Robert W.

    2007-01-01

    Since molecular energy transformations are responsible for chemical reaction rates at the most fundamental level, chemical kinetics should provide some information about molecular energies. This is the premise and objective of this note. We describe a Hamiltonian formulation for kinetic rate equations where the concentrations are the generalized coordinates and the conjugate momenta are simply related to individual average molecular energies. Simple examples are presented and the resulting en...

  8. Kinetics of the reduction of hematite (Fe{sub 2}O{sub 3}) by methane (CH{sub 4}) during chemical looping combustion: A global mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Monazam, Esmail R; Breault, Ronald W; Siriwardane, Ranjani; Richards, George; Carpenter, Stephen

    2013-10-01

    Chemical-looping combustion (CLC) has emerged as a promising technology for fossil fuel combustion which produces a sequestration ready concentrated CO{sub 2} stream in power production. A CLC system is composed with two reactors, an air and a fuel reactor. An oxygen carrier such as hematite (94%Fe{sub 2}O{sub 3}) circulates between the reactors, which transfers the oxygen necessary for the fuel combustion from the air to the fuel. An important issue for the CLC process is the selection of metal oxide as oxygen carrier, since it must retain its reactivity through many cycles. The primary objective of this work is to develop a global mechanism with respective kinetics rate parameters such that CFD simulations can be performed for large systems. In this study, thermogravimetric analysis (TGA) of the reduction of hematite (Fe{sub 2}O{sub 3}) in a continuous stream of CH{sub 4} (15, 20, and 35%) was conducted at temperatures ranging from 700 to 825{degrees}C over ten reduction cycles. The mass spectroscopy analysis of product gas indicated the presence of CO{sub 2} and H{sub 2}O at the early stage of reaction and H{sub 2} and CO at the final stage of reactions. A kinetic model based on two parallel reactions, 1) first-order irreversible rate kinetics and 2) Avrami equation describing nucleation and growth processes, was applied to the reduction data. It was found, that the reaction rates for both reactions increase with, both, temperature and the methane concentration in inlet gas.

  9. Reduction of Large Detailed Chemical Kinetic Mechanisms for Autoignition Using Joint Analyses of Reaction Rates and Sensitivities

    Energy Technology Data Exchange (ETDEWEB)

    Saylam, A; Ribaucour, M; Pitz, W J; Minetti, R

    2006-11-29

    A new technique of reduction of detailed mechanisms for autoignition, which is based on two analysis methods is described. An analysis of reaction rates is coupled to an analysis of reaction sensitivity for the detection of redundant reactions. Thresholds associated with the two analyses have a great influence on the size and efficiency of the reduced mechanism. Rules of selection of the thresholds are defined. The reduction technique has been successfully applied to detailed autoignition mechanisms of two reference hydrocarbons: n-heptane and iso-octane. The efficiency of the technique and the ability of the reduced mechanisms to reproduce well the results generated by the full mechanism are discussed. A speedup of calculations by a factor of 5.9 for n-heptane mechanism and by a factor of 16.7 for iso-octane mechanism is obtained without losing accuracy of the prediction of autoignition delay times and concentrations of intermediate species.

  10. Research in chemical kinetics, v.2

    CERN Document Server

    1994-01-01

    This is the second volume in a new series, which aims to publish authoritative review articles on a wide range of exciting and contemporary topics in gas and condensed phase kinetics. Research in Chemical Kinetics complements the acclaimed series Comprehensive Chemical Kinetics, and is edited by the same team of professionals. The reviews contained in this volume are concise, topical accounts of specific research written by acknowledged experts. The authors summarize their latest work and place it in a general context. Particular strengths of the volume are the quality of the c

  11. Research in Chemical Kinetics, v.3

    CERN Document Server

    2012-01-01

    This series of volumes aims to publish authoritative review articles on a wide range of exciting and contemporary topics in gas and condensed phase kinetics. Research in Chemical Kinetics complements the acclaimed series Comprehensive Chemical Kinetics, and is edited by the same team of professionals. The reviews contained in this volume are concise, topical accounts of specific research written by acknowledged experts. The authors summarize their latest work and place it in a general context. Particular strengths of the volume are the quality of the contributions and their top

  12. Simulation of chemical kinetics in sodium-concrete interactions

    International Nuclear Information System (INIS)

    Sodium-concrete interaction is a key safety-related issue in safety analysis of liquid metal cooled fast breeder reactors (LMFBRs). The chemical kinetics model is a key component of the sodium-concrete interaction model. Conservation equations integrated in sodium-concrete interaction model cannot be solved without a set of relationships that couple the equations together, and this may be done by the chemical kinetics model. Simultaneously, simulation of chemical kinetics is difficult due to complexity of the mechanism of chemical reactions between sodium and concrete. This paper describes the chemical kinetics simulation under some hypotheses. The chemical kinetics model was integrated with the conservation equations to form a computer code. Penetration depth, penetration rate, hydrogen flux, reaction heat, etc. can be provided by this code. Theoretical models and computational procedure were recounted in detail. Good agreements of an overall transient behavior were obtained in a series of sodium-concrete interaction experiment analysis. Comparison between analytical and experimental results showed that the chemical kinetics model presented in this paper was creditable and reasonable for simulating the sodium-concrete interactions. (authors)

  13. Simulation of chemical kinetics in sodium-concrete interactions

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Sodium-concrete interaction is a key safety-related issue in safety analysis of liquid metal cooled fast breeder reactors (LMFBRs). The chemical kinetics model is a key component of the sodium-concrete interaction model. Conservation equations integrated in sodium-concrete interaction model cannot be solved without a set of relationships that couple the equations together, and this may be done by the chemical kinetics model. Simultaneously,simulation of chemical kinetics is difficult due to complexity of the mechanism of chemical reactions between sodium and concrete. This paper describes the chemical kinetics simulation under some hypotheses. The chemical kinetics model was integrated with the conservation equations to form a computer code. Penetration depth, penetration rate,hydrogen flux, reaction heat, etc. can be provided by this code. Theoretical models and computational procedure were recounted in detail. Good agreements of an overall transient behavior were obtained in a series of sodium-concrete interaction experiment analysis. Comparison between analytical and experimental results showed that the chemical kinetics model presented in this paper was creditable and reasonable for simulating the sodium-concrete interactions.

  14. Dissolution kinetics of tuff rock and mechanism of chemical bond formation at the interface with cement grout

    International Nuclear Information System (INIS)

    The interaction of tuff rock and cement was studied to evaluate the effectiveness of sealing of tuff boreholes with cementitious grouts. Previous studies indicated chemical bond formation between tuff and cement. Dissolution studies were carried out on Topopah Spring member tuff and on tuff with cement. The results indicate the formation of calcium silicate and calcium aluminosilicate hydrates; phase identification is confirmed by XRD studies. The significance of the results obtained and their implications on properties of the interfacial region are included. 7 refs., 6 figs

  15. Chemical Kinetic Modeling of Advanced Transportation Fuels

    Energy Technology Data Exchange (ETDEWEB)

    PItz, W J; Westbrook, C K; Herbinet, O

    2009-01-20

    Development of detailed chemical kinetic models for advanced petroleum-based and nonpetroleum based fuels is a difficult challenge because of the hundreds to thousands of different components in these fuels and because some of these fuels contain components that have not been considered in the past. It is important to develop detailed chemical kinetic models for these fuels since the models can be put into engine simulation codes used for optimizing engine design for maximum efficiency and minimal pollutant emissions. For example, these chemistry-enabled engine codes can be used to optimize combustion chamber shape and fuel injection timing. They also allow insight into how the composition of advanced petroleum-based and non-petroleum based fuels affect engine performance characteristics. Additionally, chemical kinetic models can be used separately to interpret important in-cylinder experimental data and gain insight into advanced engine combustion processes such as HCCI and lean burn engines. The objectives are: (1) Develop detailed chemical kinetic reaction models for components of advanced petroleum-based and non-petroleum based fuels. These fuels models include components from vegetable-oil-derived biodiesel, oil-sand derived fuel, alcohol fuels and other advanced bio-based and alternative fuels. (2) Develop detailed chemical kinetic reaction models for mixtures of non-petroleum and petroleum-based components to represent real fuels and lead to efficient reduced combustion models needed for engine modeling codes. (3) Characterize the role of fuel composition on efficiency and pollutant emissions from practical automotive engines.

  16. Chemical Kinetic Modeling of 2-Methylhexane Combustion

    KAUST Repository

    Mohamed, Samah Y.

    2015-03-30

    Accurate chemical kinetic combustion models of lightly branched alkanes (e.g., 2-methylalkanes) are important for investigating the combustion behavior of diesel, gasoline, and aviation fuels. Improving the fidelity of existing kinetic models is a necessity, as new experiments and advanced theories show inaccuracy in certain portions of the models. This study focuses on updating thermodynamic data and kinetic model for a gasoline surrogate fuel, 2-methylhexane, with recently published group values and rate rules. These update provides a better agreement with rapid compression machine measurements of ignition delay time, while also strengthening the fundamental basis of the model.

  17. Molecular Energy Relations From Chemical Kinetics

    CERN Document Server

    Finkel, Robert W

    2007-01-01

    Since molecular energy transformations are responsible for chemical reaction rates at the most fundamental level, chemical kinetics should provide some information about molecular energies. This is the premise and objective of this note. We describe a Hamiltonian formulation for kinetic rate equations where the concentrations are the generalized coordinates and the conjugate momenta are simply related to individual average molecular energies. Simple examples are presented and the resulting energy relations naturally include non-equilibrium reactions. An analysis predicts the reasonable outcome that thermal agitation of a composite molecule increases its rate of dissociation.

  18. Air corona discharge chemical kinetics

    International Nuclear Information System (INIS)

    We have theoretically studied the initial chemical processing steps which occur in pulseless, negative, dc corona discharges in flowing air. A rate equation model is used because these discharges consist of a very small ionization zone near the pin with most of the pin-plane gap filled by a drift zone where both the electric field and the electron density are relatively uniform. The primary activated species are N2(A),O and O2(a1Δ). The predicted activated species density due to one discharge is 100 ppm per ms . mA cm2 assuming E/n=60 Td. In pure, dry air the final product due to these activated species is primarily O3. The NO /sub x/ production is about 0.5 ppm per mA. In moist air there is an additional production of about 1.5 ppm per mA of HO /sub x/ species. The predicted ozone formation reactions will be ''intercepted'' when impurities are present in the air. Impurities present at densities below about 0.1% will react primarily with the activated species rather than with electrons. Hence the predicted activated species density provides an estimate of the potential chemical processing performance of the discharge

  19. Inflation Rates, Car Devaluation, and Chemical Kinetics

    Science.gov (United States)

    Pogliani, Lionello; Berberan-Santos, Màrio N.

    1996-10-01

    The inflation rate problem of a modern economy shows quite interesting similarities with chemical kinetics and especially with first-order chemical reactions. In fact, capital devaluation during periods of rather low inflation rates or inflation measured over short periods shows a dynamics formally similar to that followed by first-order chemical reactions and they can thus be treated by the aid of the same mathematical formalism. Deviations from this similarity occurs for higher inflation rates. The dynamics of price devaluation for two different types of car, a compact car and a luxury car, has been followed for seven years long and it has been established that car devaluation is a process that is formally similar to a zeroth-order chemical kinetic process disregarding the type of car, if car devaluation is much faster than money devaluation. In fact, expensive cars devaluate with a faster rate than inexpensive cars.

  20. Fundamental aspects of plasma chemical physics kinetics

    CERN Document Server

    Capitelli, Mario; Colonna, Gianpiero; Esposito, Fabrizio; Gorse, Claudine; Hassouni, Khaled; Laricchiuta, Annarita; Longo, Savino

    2016-01-01

    Describing non-equilibrium "cold" plasmas through a chemical physics approach, this book uses the state-to-state plasma kinetics, which considers each internal state as a new species with its own cross sections. Extended atomic and molecular master equations are coupled with Boltzmann and Monte Carlo methods to solve the electron energy distribution function. Selected examples in different applied fields, such as microelectronics, fusion, and aerospace, are presented and discussed including the self-consistent kinetics in RF parallel plate reactors, the optimization of negative ion sources and the expansion of high enthalpy flows through nozzles of different geometries. The book will cover the main aspects of the state-to-state kinetic approach for the description of nonequilibrium cold plasmas, illustrating the more recent achievements in the development of kinetic models including the self-consistent coupling of master equations and Boltzmann equation for electron dynamics. To give a complete portrayal, the...

  1. Stochastic Chemical Kinetics with Energy Parameters

    CERN Document Server

    Fayolle, Guy; Pirogov, Serguei

    2011-01-01

    Abstact: We introduce new models of energy redistribution in stochastic chemical kinetics with several molecule types and energy parameters. The main results concern the situations when there are product form measures. Using a probabilistic interpretation of the related Boltzmann equation, we find some invariant measures explicitly and prove convergence to them.

  2. CHEMSIMUL: A simulator for chemical kinetics

    DEFF Research Database (Denmark)

    Kirkegaard, P.; Bjergbakke, E.

    1999-01-01

    CHEMSIMUL is a computer program system for numerical simulation of chemical reaction systems. It can be used for modeling complex kinetics in many contexts, in particular radiolytic processes. It contains a translator module and a module for solving theresulting coupled nonlinear ordinary...

  3. Chemical Dosing and First-Order Kinetics

    Science.gov (United States)

    Hladky, Paul W.

    2011-01-01

    College students encounter a variety of first-order phenomena in their mathematics and science courses. Introductory chemistry textbooks that discuss first-order processes, usually in conjunction with chemical kinetics or radioactive decay, stop at single, discrete dose events. Although single-dose situations are important, multiple-dose events,…

  4. Chemical kinetic modeling of H{sub 2} applications

    Energy Technology Data Exchange (ETDEWEB)

    Marinov, N.M.; Westbrook, C.K.; Cloutman, L.D. [Lawrence Livermore National Lab., CA (United States)] [and others

    1995-09-01

    Work being carried out at LLNL has concentrated on studies of the role of chemical kinetics in a variety of problems related to hydrogen combustion in practical combustion systems, with an emphasis on vehicle propulsion. Use of hydrogen offers significant advantages over fossil fuels, and computer modeling provides advantages when used in concert with experimental studies. Many numerical {open_quotes}experiments{close_quotes} can be carried out quickly and efficiently, reducing the cost and time of system development, and many new and speculative concepts can be screened to identify those with sufficient promise to pursue experimentally. This project uses chemical kinetic and fluid dynamic computational modeling to examine the combustion characteristics of systems burning hydrogen, either as the only fuel or mixed with natural gas. Oxidation kinetics are combined with pollutant formation kinetics, including formation of oxides of nitrogen but also including air toxics in natural gas combustion. We have refined many of the elementary kinetic reaction steps in the detailed reaction mechanism for hydrogen oxidation. To extend the model to pressures characteristic of internal combustion engines, it was necessary to apply theoretical pressure falloff formalisms for several key steps in the reaction mechanism. We have continued development of simplified reaction mechanisms for hydrogen oxidation, we have implemented those mechanisms into multidimensional computational fluid dynamics models, and we have used models of chemistry and fluid dynamics to address selected application problems. At the present time, we are using computed high pressure flame, and auto-ignition data to further refine the simplified kinetics models that are then to be used in multidimensional fluid mechanics models. Detailed kinetics studies have investigated hydrogen flames and ignition of hydrogen behind shock waves, intended to refine the detailed reactions mechanisms.

  5. Perspective: Stochastic algorithms for chemical kinetics.

    Science.gov (United States)

    Gillespie, Daniel T; Hellander, Andreas; Petzold, Linda R

    2013-05-01

    We outline our perspective on stochastic chemical kinetics, paying particular attention to numerical simulation algorithms. We first focus on dilute, well-mixed systems, whose description using ordinary differential equations has served as the basis for traditional chemical kinetics for the past 150 years. For such systems, we review the physical and mathematical rationale for a discrete-stochastic approach, and for the approximations that need to be made in order to regain the traditional continuous-deterministic description. We next take note of some of the more promising strategies for dealing stochastically with stiff systems, rare events, and sensitivity analysis. Finally, we review some recent efforts to adapt and extend the discrete-stochastic approach to systems that are not well-mixed. In that currently developing area, we focus mainly on the strategy of subdividing the system into well-mixed subvolumes, and then simulating diffusional transfers of reactant molecules between adjacent subvolumes together with chemical reactions inside the subvolumes.

  6. Perspective: Stochastic algorithms for chemical kinetics

    Science.gov (United States)

    Gillespie, Daniel T.; Hellander, Andreas; Petzold, Linda R.

    2013-05-01

    We outline our perspective on stochastic chemical kinetics, paying particular attention to numerical simulation algorithms. We first focus on dilute, well-mixed systems, whose description using ordinary differential equations has served as the basis for traditional chemical kinetics for the past 150 years. For such systems, we review the physical and mathematical rationale for a discrete-stochastic approach, and for the approximations that need to be made in order to regain the traditional continuous-deterministic description. We next take note of some of the more promising strategies for dealing stochastically with stiff systems, rare events, and sensitivity analysis. Finally, we review some recent efforts to adapt and extend the discrete-stochastic approach to systems that are not well-mixed. In that currently developing area, we focus mainly on the strategy of subdividing the system into well-mixed subvolumes, and then simulating diffusional transfers of reactant molecules between adjacent subvolumes together with chemical reactions inside the subvolumes.

  7. 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.

  8. CATALYTIC COMBUSTION OF METHANE OVER Pt/γ-Al2O3 IN MICRO-COMBUSTOR WITH DETAILED CHEMICAL KINETIC MECHANISMS

    Directory of Open Access Journals (Sweden)

    JUNJIE CHEN

    2014-11-01

    Full Text Available Micro-scale catalytic combustion characteristics and heat transfer processes of preheated methane-air mixtures (φ = 0.4 in the plane channel were investigated numerically with detailed chemical kinetic mechanisms. The plane channel of length L = 10.0 mm, height H =1.0 mm and wall thickness δ = 0.1 mm, which inner horizontal surfaces contained Pt/γ-Al2O3 catalyst washcoat. The computational results indicate that the presence of the gas phase reactions extends mildly the micro-combustion stability limits at low and moderate inlet velocities due to the strong flames establishment, and have a more profound effect on extending the high-velocity blowout limits by allowing for additional heat release originating mainly from the incomplete CH4 gas phase oxidation in the plane channel. When the same mass flow rate (ρin × Vin is considered, the micro-combustion stability limits at p: 0.1 MPa are much narrower than at p: 0.6 MPa due to both gas phase and catalytic reaction activities decline with decreasing pressure. Catalytic micro-combustor can achieve stable combustion at low solid thermal conductivity ks < 0.1 W∙m-1•K-1, while the micro-combustion extinction limits reach their larger extent for the higher thermal conductivity ks = 20.0-100.0 W∙m-1•K-1. The existence of surface radiation heat transfers significantly effects on the micro-combustion stability limits and micro-combustors energy balance. Finally, gas phase combustion in catalytic micro-combustors can be sustained at the sub-millimeter scale (plane channel height of 0.25 mm.

  9. The Multiplexed Chemical Kinetic Photoionization Mass Spectrometer: A New Approach To Isomer-resolved Chemical Kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Osborne, David L.; Zou, Peng; Johnsen, Howard; Hayden, Carl C.; Taatjes, Craig A.; Knyazev, Vadim D.; North, Simon W.; Peterka, Darcy S.; Ahmed, Musahid; Leone, Stephen R.

    2008-08-28

    We have developed a multiplexed time- and photon-energy?resolved photoionizationmass spectrometer for the study of the kinetics and isomeric product branching of gasphase, neutral chemical reactions. The instrument utilizes a side-sampled flow tubereactor, continuously tunable synchrotron radiation for photoionization, a multi-massdouble-focusing mass spectrometer with 100percent duty cycle, and a time- and positionsensitive detector for single ion counting. This approach enables multiplexed, universal detection of molecules with high sensitivity and selectivity. In addition to measurement of rate coefficients as a function of temperature and pressure, different structural isomers can be distinguished based on their photoionization efficiency curves, providing a more detailed probe of reaction mechanisms. The multiplexed 3-dimensional data structure (intensity as a function of molecular mass, reaction time, and photoionization energy) provides insights that might not be available in serial acquisition, as well as additional constraints on data interpretation.

  10. Stochastic Chemical Kinetics with Energy Parameters

    OpenAIRE

    Fayolle, Guy; Malyshev, Vadim A.; Pirogov, Serguei

    2004-01-01

    International audience Abstact: We introduce new models of energy redistribution in stochastic chemical kinetics with several molecule types and energy parameters. The main results concern the situations when there are product form measures. Using a probabilistic interpretation of the related Boltzmann equation, we find some invariant measures explicitly and prove convergence to them. Résumé : Nous introduisons de nouveaux modèles de réseaus de cinétique chimique, avec plusieurs types d...

  11. Chemical Dynamics, Molecular Energetics, and Kinetics at the Synchrotron

    Energy Technology Data Exchange (ETDEWEB)

    Leone, Stephen R.; Ahmed, Musahid; Wilson, Kevin R.

    2010-03-14

    Scientists at the Chemical Dynamics Beamline of the Advanced Light Source in Berkeley are continuously reinventing synchrotron investigations of physical chemistry and chemical physics with vacuum ultraviolet light. One of the unique aspects of a synchrotron for chemical physics research is the widely tunable vacuum ultraviolet light that permits threshold ionization of large molecules with minimal fragmentation. This provides novel opportunities to assess molecular energetics and reaction mechanisms, even beyond simple gas phase molecules. In this perspective, significant new directions utilizing the capabilities at the Chemical Dynamics Beamline are presented, along with an outlook for future synchrotron and free electron laser science in chemical dynamics. Among the established and emerging fields of investigations are cluster and biological molecule spectroscopy and structure, combustion flame chemistry mechanisms, radical kinetics and product isomer dynamics, aerosol heterogeneous chemistry, planetary and interstellar chemistry, and secondary neutral ion-beam desorption imaging of biological matter and materials chemistry.

  12. Chemical Kinetics of Hydrocarbon Ignition in Practical Combustion Systems

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C.K.

    2000-07-07

    Chemical kinetic factors of hydrocarbon oxidation are examined in a variety of ignition problems. Ignition is related to the presence of a dominant chain branching reaction mechanism that can drive a chemical system to completion in a very short period of time. Ignition in laboratory environments is studied for problems including shock tubes and rapid compression machines. Modeling of the laboratory systems are used to develop kinetic models that can be used to analyze ignition in practical systems. Two major chain branching regimes are identified, one consisting of high temperature ignition with a chain branching reaction mechanism based on the reaction between atomic hydrogen with molecular oxygen, and the second based on an intermediate temperature thermal decomposition of hydrogen peroxide. Kinetic models are then used to describe ignition in practical combustion environments, including detonations and pulse combustors for high temperature ignition, and engine knock and diesel ignition for intermediate temperature ignition. The final example of ignition in a practical environment is homogeneous charge, compression ignition (HCCI) which is shown to be a problem dominated by the kinetics intermediate temperature hydrocarbon ignition. Model results show why high hydrocarbon and CO emissions are inevitable in HCCI combustion. The conclusion of this study is that the kinetics of hydrocarbon ignition are actually quite simple, since only one or two elementary reactions are dominant. However, there are many combustion factors that can influence these two major reactions, and these are the features that vary from one practical system to another.

  13. Chemical kinetics and combustion modelling with CFX 4

    Energy Technology Data Exchange (ETDEWEB)

    Stopford, P. [AEA Technology, Computational Fluid Dynamics Services Harwell, Oxfordshire (United Kingdom)

    1997-12-31

    The presentation describes some recent developments in combustion and kinetics models used in the CFX software of AEA Technology. Three topics are highlighted: the development of coupled solvers in a traditional `SIMPLE`-based CFD code, the use of detailed chemical kinetics mechanism via `look-up` tables and the application of CFD to large-scale multi-burner combustion plant. The aim is identify those physical approximations and numerical methods that are likely to be most useful in the future and those areas where further developments are required. (author) 6 refs.

  14. Chemical kinetic modeling of H{sub 2} applications

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C.K.; Marinov, N.; Pitz, W.J.; Curran, H. [Lawrence Livermore National Lab., CA (United States)

    1996-10-01

    This project is intended to develop detailed and simplified kinetic reaction mechanisms for the combustion of practical systems fueled by hydrogen, and then to use those mechanisms to examine the performance, efficiency, pollutant emissions, and other characteristics of those systems. During the last year, a H2/NOx mechanism has been developed that gives much improved predictions of NOx emissions compared to experimental data. Preliminary chemical kinetic and equilibrium calculations have been performed in support of Br2-H2O experiments to be conducted at NREL. Hydrogen, hydrogen/methane and hydrogen/natural gas mixtures have been investigated in a knock-rating engine to assess their automotive knock characteristics. The authors are currently developing the simplified analog reaction mechanisms that are computationally simple, yet still reproduce many of the macroscopic features of flame propagation.

  15. 菜籽油生物柴油化学动力学机理的构建%Construction of Chemical Kinetics Mechanism for Rapeseed Oil Biodiesel

    Institute of Scientific and Technical Information of China (English)

    毛功平; 王忠; 倪培永

    2014-01-01

    The ester components and their proportion of biodiesel fuel prepared by rapesee d oil were measured by gas chroma‐tography‐mass spectrometry and the molecular formula of biodiesel fuel was fitted according to the formula and content of main components .Then the prepared biodiesel was taken place by the equivalent blended fuel of methyl butyrate and n‐heptane and hence a new biodiesel chemical kinetic mechanism was constructed by superposition method .According to the sensitivity to ele‐mentary reaction of main pollutant formation ,the elementary reaction that needed to be corrected was screened .The chemical reaction rate constant was corrected by adjusting the pre‐exponential factor and then the mole fraction of CO2 and C2 H4 under different disturbance was also simulated .The average error between simulated and experimental results was analyzed .The re‐sults show that the fitting formula of biodiesel fuel is C19 H36 O2 .The molecular formula ,molecular weight and viscosity of blended fuel are closer to actual biodiesel compared with methyl butyrate and can be used as biodiesel .Due to the slight increase of pre‐exponential factor ,the average error for CO2 and C2 H4 mole fraction are both very small .%采用气‐质联用仪测量了以菜籽油为原料制备的生物柴油的酯类组成成分和比例,根据主要组分的分子式和含量,拟合得到生物柴油的分子式。确定了以丁酸甲酯和正庚烷组成的混合燃料来替代生物柴油,采用“叠加法”构建得到一种新的生物柴油化学动力学机理。通过对影响主要污染物生成的基元反应进行敏感性分析,筛选出新机理中需要修正的基元反应。调整指前因子修正化学反应速率常数,模拟不同扰动下CO2和C2 H4的摩尔分数,分析模拟结果与试验结果的平均误差。研究结果表明:生物柴油的拟合分子式为C19 H36 O2;丁酸甲酯和正庚烷组成的混合燃料在分子式、分

  16. Mechano-chemical energy transduction in biological systems. The effect of mechanical stimulation on the polymerization of actin: a kinetic study.

    Science.gov (United States)

    Ferri, A; Grazi, E

    1982-01-01

    Mechanical stimulation (forced circulation in narrow tubing) accelerates as much as 10-fold the rate of polymerization of actin. The increase in the rate is proportional to the intensity of the stimulation for flow rates between 0 and 3 cm/s. This supports the hypothesis that a statistical factor (the orientation of the flowing particles) is influenced by the flow. Comparison of the kinetics of the polymerization of resting and of mechanically stimulated actin solutions shows that both the nucleation and the elongation steps are accelerated. It is thus concluded that flow orients not only the oligomeric structures but also the actin monomers. The elongation reaction, also in the flow-stimulated samples, occurs always by the addition of ATP--G-actin (or ATP-containing oligomers) and not by the fusion of ADP-containing oligomeric structures. PMID:7138502

  17. A kinetic model for chemical neurotransmission

    Science.gov (United States)

    Ramirez-Santiago, Guillermo; Martinez-Valencia, Alejandro; Fernandez de Miguel, Francisco

    Recent experimental observations in presynaptic terminals at the neuromuscular junction indicate that there are stereotyped patterns of cooperativeness in the fusion of adjacent vesicles. That is, a vesicle in hemifusion process appears on the side of a fused vesicle and which is followed by another vesicle in a priming state while the next one is in a docking state. In this talk we present a kinetic model for this morphological pattern in which each vesicle state previous to the exocytosis is represented by a kinetic state. This chain states kinetic model can be analyzed by means of a Master equation whose solution is simulated with the stochastic Gillespie algorithm. With this approach we have reproduced the responses to the basal release in the absence of stimulation evoked by the electrical activity and the phenomena of facilitation and depression of neuromuscular synapses. This model offers new perspectives to understand the underlying phenomena in chemical neurotransmission based on molecular interactions that result in the cooperativity between vesicles during neurotransmitter release. DGAPA Grants IN118410 and IN200914 and Conacyt Grant 130031.

  18. On the theory of time dilation in chemical kinetics

    CERN Document Server

    Baig, Mirza Wasif

    2012-01-01

    The rates of chemical reactions are not absolute but their magnitude depends upon the relative speeds of the moving observers. This has been proved by unifying theories of chemical kinetics, which are transition state theory, collision theory and Marcus theory, with the special theory of relativity. Lorentz transformations of Boltzmann constant and energy spacing between permitted quantum levels of molecules are quantum mechanically proved to be Lorentz variant. The relativistic statistical thermodynamics has been developed to explain quasiequilibrium existing between reactants and activated complex. The newly formulated Lorentz transformation of the rate constant from Arrhenius Equation, of the collision frequency and of the Eyring and Marcus equations renders the rate law also Lorentz variant. For a moving observer moving at fractions of the speed of light along the reaction coordinate the transition state possess less kinetic energy to sweep translation over it. This results in the slower transformation of...

  19. A fundamental research on combustion chemical kinetic model’s precision property

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Uncertainty analysis was used to investigate the precision property of detailed chemical kinetic models.A general-purpose algorithm for assessing and evaluating the impact of uncertainties in chemical kinetic models is presented.The method was also validated through analysis of different kinetic mechanisms applied in the process of modeling NOx emission in methane flame. The algorithm,which provided a basis for further studies,was more efficient and general compared with other methods.

  20. Oxygen-18 kinetic isotope effects in the dopamine beta-monooxygenase reaction: evidence for a new chemical mechanism in non-heme metallomonooxygenases.

    Science.gov (United States)

    Tian, G; Berry, J A; Klinman, J P

    1994-01-11

    Previous studies of dopamine beta-monooxygenase (D beta M) have implicated the formation of a substrate-derived benzylic radical via a hydrogen atom abstraction mechanism [Miller & Klinman (1985) Biochemistry 24, 2114]. We now address the nature of the oxygen species catalyzing C-H bond cleavage through the measurement of oxygen-18 isotope effects as a function of substrate structure. Using deuterium isotope effects, together with experimental O-18 isotope effects with protonated and deuterated substrates, it has been possible to calculate intrinsic O-18 isotope effects. Since the D beta M mechanism includes many steps which may involve changes in bond order at dioxygen, e.g., the reversible binding of O2 to the active-site copper and its reductive activation to a copper-hydroperoxide species, the intrinsic O-18 isotope effect is expected to be the product of two terms: (1) an overall equilibrium O-18 isotope effect on steps leading from O2 binding to the formation of the intermediate which catalyzes C-H bond cleavage and (2) a kinetic O-18 isotope effect on the C-H bond cleavage step. Thus, the magnitude of a single O-18 isotope effect measurement cannot reveal the nature of the bonding at oxygen during substrate activation. In the present study we have measured the change in O-18 isotope effect as a function of substrate structure and reactivity, finding values of 18(V/K) which decrease from 1.0281 +/- 0.001 to 1.0216 +/- 0.0003 as the rate of the C-H bond cleavage step decreases from 680 to 2 s-1.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:8286345

  1. Theory of the Kinetics of Chemical Potentials in Heterogeneous Catalysis

    OpenAIRE

    Cheng, Jun; Hu, P

    2011-01-01

    Simple and powerful: The reaction kinetics at surfaces of heterogeneous catalysts is reformulated in terms of the involved chemical potentials. Based on this formulism, an approach of searching for good catalysts is proposed without recourse to extensive calculations of reaction barriers and detailed kinetic analyses. (see picture; R=reactant, I=surface intermediate, P=product, and =standard chemical potential).

  2. Kinetic partitioning mechanism of HDV ribozyme folding

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Jiawen; Gong, Sha; Wang, Yujie; Zhang, Wenbing, E-mail: wbzhang@whu.edu.cn [Department of Physics, Wuhan University, Wuhan, Hubei 430072 (China)

    2014-01-14

    RNA folding kinetics is directly tied to RNA biological functions. We introduce here a new approach for predicting the folding kinetics of RNA secondary structure with pseudoknots. This approach is based on our previous established helix-based method for predicting the folding kinetics of RNA secondary structure. In this approach, the transition rates for an elementary step: (1) formation, (2) disruption of a helix stem, and (3) helix formation with concomitant partial melting of an incompatible helix, are calculated with the free energy landscape. The folding kinetics of the Hepatitis delta virus (HDV) ribozyme and the mutated sequences are studied with this method. The folding pathways are identified by recursive searching the states with high net flux-in(out) population starting from the native state. The theory results are in good agreement with that of the experiments. The results indicate that the bi-phasic folding kinetics for the wt HDV sequence is ascribed to the kinetic partitioning mechanism: Part of the population will quickly fold to the native state along the fast pathway, while another part of the population will fold along the slow pathway, in which the population is trapped in a non-native state. Single mutation not only changes the folding rate but also the folding pathway.

  3. pyJac: analytical Jacobian generator for chemical kinetics

    CERN Document Server

    Niemeyer, Kyle E; Sung, Chih-Jen

    2016-01-01

    Accurate simulations of combustion phenomena require the use of detailed chemical kinetics in order to capture limit phenomena such as ignition and extinction as well as predict pollutant formation. However, the chemical kinetic models for hydrocarbon fuels of practical interest typically have large numbers of species and reactions and exhibit high levels of mathematical stiffness in the governing differential equations, particularly for larger fuel molecules. In order to integrate the stiff equations governing chemical kinetics, generally reactive-flow simulations rely on implicit algorithms that require frequent Jacobian matrix evaluations. Some in situ and a posteriori computational diagnostics methods also require accurate Jacobian matrices, including computational singular perturbation and chemical explosive mode analysis. Typically, finite differences numerically approximate these, but for larger chemical kinetic models this poses significant computational demands since the number of chemical source ter...

  4. Redox kinetics and mechanism in silicate melts

    International Nuclear Information System (INIS)

    This work contributes to better understand iron redox reactions and mechanisms in silicate melts. It was conducted on compositions in both Na2O-B2O3-SiO2-FeO and Na2O-Al2O3-SiO2-FeO systems. The influence of boron-sodium and aluminum-sodium substitutions and iron content on properties and structure of glasses and on the iron redox kinetics has been studied by Raman, Moessbauer and XANES spectroscopies at the B and Fe K-edges. In borosilicate glasses, an increase in iron content or in the Fe3+/ΣFe redox state implies a structural rearrangement of the BO4 species in the glass network whereas the BO3 and BO4 relative proportions remain nearly constant. In all studied glasses and melts, Fe3+ is a network former in tetrahedral coordination, unless for aluminosilicates of ratio Al/Na≥1 where Fe3+ is a network modifier in five-fold coordination. Near Tg, diffusion of network modifying cations controls the iron redox kinetics along with a flux of electron holes. At liquidus temperatures, oxygen diffusion is considered to be the mechanism that governs redox reactions. This study shows the role played by the silicate network polymerization on the redox kinetics. In borosilicate melts, iron redox kinetics depends on the boron speciation between BO3 and BO4 that depends itself on the sodium content. Furthermore, an increase in the network-former/network-modifier ratio implies a decrease in oxygen diffusion that results in a slowing down of the redox kinetics. The obtained results allow a description of the iron redox kinetics for more complex compositions as natural lavas or nuclear waste model glasses. (author)

  5. Empiricism or self-consistent theory in chemical kinetics?

    International Nuclear Information System (INIS)

    To give theoretical background for mechanochemical kinetics, we need first of all to find a possibility to predict the kinetic parameters for real chemical processes by determining rate constants and reaction orders without developing strictly specialized and, to a great extent, artificial models, i.e. to derive the kinetic law of mass action from 'first principles'. However, the kinetic law of mass action has had only an empirical basis from the first experiments of Gulberg and Waage until now, in contrast to the classical law of mass action for chemical equilibrium rigorously derived in chemical thermodynamics from equilibrium condition. Nevertheless, in this paper, an attempt to derive the kinetic law of mass action from 'first principles' is made in macroscopic formulation. It has turned out to be possible owing to the methods of thermodynamics of irreversible processes that were unknown in Gulberg and Waage's time

  6. A brief review of the use of environmental chambers for gas phase studies of kinetics, chemical mechanisms and characterisation of field instruments

    OpenAIRE

    Seakins P.W.

    2010-01-01

    This introductory review considers the role of environmental chambers in atmospheric chemistry, emphasising the importance of being able to carry out studies in controlled conditions. The advantages and disadvantages of different types of chambers are discussed and compared. Examples of the use of chambers for kinetic and mechanistic studies are presented. The final section of this brief review considers the use of chambers in providing a well defined environment for calibrating and investiga...

  7. A brief review of the use of environmental chambers for gas phase studies of kinetics, chemical mechanisms and characterisation of field instruments

    Directory of Open Access Journals (Sweden)

    Seakins P.W.

    2010-12-01

    Full Text Available This introductory review considers the role of environmental chambers in atmospheric chemistry, emphasising the importance of being able to carry out studies in controlled conditions. The advantages and disadvantages of different types of chambers are discussed and compared. Examples of the use of chambers for kinetic and mechanistic studies are presented. The final section of this brief review considers the use of chambers in providing a well defined environment for calibrating and investigating the performance of field instruments.

  8. 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…

  9. Compact Kinetic Mechanisms for Petroleum-Derived and Alternative Aviation Fuels Project

    Data.gov (United States)

    National Aeronautics and Space Administration — To be useful for computational combustor design and analysis using tools like the National Combustion Code (NCC), low-dimensional chemical kinetic mechanisms for...

  10. CHEMKIN-III: A FORTRAN chemical kinetics package for the analysis of gas-phase chemical and plasma kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Kee, R.J.; Rupley, F.M.; Meeks, E.; Miller, J.A.

    1996-05-01

    This document is the user`s manual for the third-generation CHEMKIN package. CHEMKIN is a software package whose purpose is to facilitate the formation, solution, and interpretation of problems involving elementary gas-phase chemical kinetics. It provides a flexible and powerful tool for incorporating complex chemical kinetics into simulations of fluid dynamics. The package consists of two major software components: an Interpreter and a Gas-Phase Subroutine Library. The Interpreter is a program that reads a symbolic description of an elementary, user-specified chemical reaction mechanism. One output from the Interpreter is a data file that forms a link to the Gas-Phase Subroutine Library. This library is a collection of about 100 highly modular FORTRAN subroutines that may be called to return information on equations of state, thermodynamic properties, and chemical production rates. CHEMKIN-III includes capabilities for treating multi-fluid plasma systems, that are not in thermal equilibrium. These new capabilities allow researchers to describe chemistry systems that are characterized by more than one temperature, in which reactions may depend on temperatures associated with different species; i.e. reactions may be driven by collisions with electrons, ions, or charge-neutral species. These new features have been implemented in such a way as to require little or no changes to CHEMKIN implementation for systems in thermal equilibrium, where all species share the same gas temperature. CHEMKIN-III now has the capability to handle weakly ionized plasma chemistry, especially for application related to advanced semiconductor processing.

  11. High Temperature Chemical Kinetic Combustion Modeling of Lightly Methylated Alkanes

    Energy Technology Data Exchange (ETDEWEB)

    Sarathy, S M; Westbrook, C K; Pitz, W J; Mehl, M

    2011-03-01

    Conventional petroleum jet and diesel fuels, as well as alternative Fischer-Tropsch (FT) fuels and hydrotreated renewable jet (HRJ) fuels, contain high molecular weight lightly branched alkanes (i.e., methylalkanes) and straight chain alkanes (n-alkanes). Improving the combustion of these fuels in practical applications requires a fundamental understanding of large hydrocarbon combustion chemistry. This research project presents a detailed high temperature chemical kinetic mechanism for n-octane and three lightly branched isomers octane (i.e., 2-methylheptane, 3-methylheptane, and 2,5-dimethylhexane). The model is validated against experimental data from a variety of fundamental combustion devices. This new model is used to show how the location and number of methyl branches affects fuel reactivity including laminar flame speed and species formation.

  12. Studies of combustion kinetics and mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Gutman, D. [Catholic Univ. of America, Washington, DC (United States)

    1993-12-01

    The objective of the current research is to gain new quantitative knowledge of the kinetics and mechanisms of polyatomic free radicals which are important in hydrocarbon combustion processes. The special facility designed and built for these (which includes a heatable tubular reactor coupled to a photoionization mass spectrometer) is continually being improved. Where possible, these experimental studies are coupled with theoretical ones, sometimes conducted in collaboration with others, to obtain an improved understanding of the factors determining reactivity. The decomposition of acetyl radicals, isopropyl radicals, and n-propyl radicals have been studied as well as the oxidation of methylpropargyl radicals.

  13. Optimization of KINETICS Chemical Computation Code

    Science.gov (United States)

    Donastorg, Cristina

    2012-01-01

    NASA JPL has been creating a code in FORTRAN called KINETICS to model the chemistry of planetary atmospheres. Recently there has been an effort to introduce Message Passing Interface (MPI) into the code so as to cut down the run time of the program. There has been some implementation of MPI into KINETICS; however, the code could still be more efficient than it currently is. One way to increase efficiency is to send only certain variables to all the processes when an MPI subroutine is called and to gather only certain variables when the subroutine is finished. Therefore, all the variables that are used in three of the main subroutines needed to be investigated. Because of the sheer amount of code that there is to comb through this task was given as a ten-week project. I have been able to create flowcharts outlining the subroutines, common blocks, and functions used within the three main subroutines. From these flowcharts I created tables outlining the variables used in each block and important information about each. All this information will be used to determine how to run MPI in KINETICS in the most efficient way possible.

  14. Hungarian University Students' Misunderstandings in Thermodynamics and Chemical Kinetics

    Science.gov (United States)

    Turanyi, Tamas; Toth, Zoltan

    2013-01-01

    The misunderstandings related to thermodynamics (including chemical equilibrium) and chemical kinetics of first and second year Hungarian students of chemistry, environmental science, biology and pharmacy were investigated. We demonstrated that Hungarian university students have similar misunderstandings in physical chemistry to those reported in…

  15. NDMA formation by chloramination of ranitidine: Kinetics and mechanism

    KAUST Repository

    Le Roux, Julien

    2012-10-16

    The kinetics of decomposition of the pharmaceutical ranitidine (a major precursor of NDMA) during chloramination was investigated and some decomposition byproducts were identified by using high performance liquid chromatography coupled with mass spectrometry (HPLC-MS). The reaction between monochloramine and ranitidine followed second order kinetics and was acid-catalyzed. Decomposition of ranitidine formed different byproducts depending on the applied monochloramine concentration. Most identified products were chlorinated and hydroxylated analogues of ranitidine. In excess of monochloramine, nucleophilic substitution between ranitidine and monochloramine led to byproducts that are critical intermediates involved in the formation of NDMA, for example, a carbocation formed from the decomposition of the methylfuran moiety of ranitidine. A complete mechanism is proposed to explain the high formation yield of NDMA from chloramination of ranitidine. These results are of great importance to understand the formation of NDMA by chloramination of tertiary amines. © 2012 American Chemical Society.

  16. The thermodynamic natural path in chemical reaction kinetics

    Directory of Open Access Journals (Sweden)

    Moishe garfinkle

    2000-01-01

    Full Text Available The Natural Path approach to chemical reaction kinetics was developed to bridge the considerable gap between the Mass Action mechanistic approach and the non-mechanistic irreversible thermodynamic approach. The Natural Path approach can correlate empirical kinetic data with a high degree precision, as least equal to that achievable by the Mass-Action rate equations, but without recourse mechanistic considerations. The reaction velocities arising from the particular rate equation chosen by kineticists to best represent the kinetic behavior of a chemical reaction are the natural outcome of the Natural Path approach. Moreover, by virtue of its thermodynamic roots, equilibrium thermodynamic functions can be extracted from reaction kinetic data with considerable accuracy. These results support the intrinsic validity of the Natural Path approach.

  17. Chemical, physical, and theoretical kinetics of an ultrafast folding protein.

    Science.gov (United States)

    Kubelka, Jan; Henry, Eric R; Cellmer, Troy; Hofrichter, James; Eaton, William A

    2008-12-01

    An extensive set of equilibrium and kinetic data is presented and analyzed for an ultrafast folding protein--the villin subdomain. The equilibrium data consist of the excess heat capacity, tryptophan fluorescence quantum yield, and natural circular-dichroism spectrum as a function of temperature, and the kinetic data consist of time courses of the quantum yield from nanosecond-laser temperature-jump experiments. The data are well fit with three kinds of models--a three-state chemical-kinetics model, a physical-kinetics model, and an Ising-like theoretical model that considers 10(5) possible conformations (microstates). In both the physical-kinetics and theoretical models, folding is described as diffusion on a one-dimensional free-energy surface. In the physical-kinetics model the reaction coordinate is unspecified, whereas in the theoretical model, order parameters, either the fraction of native contacts or the number of native residues, are used as reaction coordinates. The validity of these two reaction coordinates is demonstrated from calculation of the splitting probability from the rate matrix of the master equation for all 10(5) microstates. The analysis of the data on site-directed mutants using the chemical-kinetics model provides information on the structure of the transition-state ensemble; the physical-kinetics model allows an estimate of the height of the free-energy barrier separating the folded and unfolded states; and the theoretical model provides a detailed picture of the free-energy surface and a residue-by-residue description of the evolution of the folded structure, yet contains many fewer adjustable parameters than either the chemical- or physical-kinetics models.

  18. Chemical Kinetic Models for HCCI and Diesel Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Pitz, W J; Westbrook, C K; Mehl, M; Sarathy, S M

    2010-11-15

    Predictive engine simulation models are needed to make rapid progress towards DOE's goals of increasing combustion engine efficiency and reducing pollutant emissions. These engine simulation models require chemical kinetic submodels to allow the prediction of the effect of fuel composition on engine performance and emissions. Chemical kinetic models for conventional and next-generation transportation fuels need to be developed so that engine simulation tools can predict fuel effects. The objectives are to: (1) Develop detailed chemical kinetic models for fuel components used in surrogate fuels for diesel and HCCI engines; (2) Develop surrogate fuel models to represent real fuels and model low temperature combustion strategies in HCCI and diesel engines that lead to low emissions and high efficiency; and (3) Characterize the role of fuel composition on low temperature combustion modes of advanced combustion engines.

  19. Thermodynamically consistent model calibration in chemical kinetics

    Directory of Open Access Journals (Sweden)

    Goutsias John

    2011-05-01

    Full Text Available Abstract Background The dynamics of biochemical reaction systems are constrained by the fundamental laws of thermodynamics, which impose well-defined relationships among the reaction rate constants characterizing these systems. Constructing biochemical reaction systems from experimental observations often leads to parameter values that do not satisfy the necessary thermodynamic constraints. This can result in models that are not physically realizable and may lead to inaccurate, or even erroneous, descriptions of cellular function. Results We introduce a thermodynamically consistent model calibration (TCMC method that can be effectively used to provide thermodynamically feasible values for the parameters of an open biochemical reaction system. The proposed method formulates the model calibration problem as a constrained optimization problem that takes thermodynamic constraints (and, if desired, additional non-thermodynamic constraints into account. By calculating thermodynamically feasible values for the kinetic parameters of a well-known model of the EGF/ERK signaling cascade, we demonstrate the qualitative and quantitative significance of imposing thermodynamic constraints on these parameters and the effectiveness of our method for accomplishing this important task. MATLAB software, using the Systems Biology Toolbox 2.1, can be accessed from http://www.cis.jhu.edu/~goutsias/CSS lab/software.html. An SBML file containing the thermodynamically feasible EGF/ERK signaling cascade model can be found in the BioModels database. Conclusions TCMC is a simple and flexible method for obtaining physically plausible values for the kinetic parameters of open biochemical reaction systems. It can be effectively used to recalculate a thermodynamically consistent set of parameter values for existing thermodynamically infeasible biochemical reaction models of cellular function as well as to estimate thermodynamically feasible values for the parameters of new

  20. Mechanisms of multiple chemical sensitivity.

    Science.gov (United States)

    Winder, Chris

    2002-03-10

    Sensitivity to chemicals is a toxicological concept, contained in the dose-response relationship. Sensitivity also includes the concept of hypersensitivity, although controversy surrounds the nature of effects from very low exposures. The term multiple chemical sensitivity has been used to describe individuals with a debilitating, multi-organ sensitivity following chemical exposures. Many aspects of this condition extend the nature of sensitivity to low levels of exposure to chemicals, and is a designation with medical, immunological, neuropsychological and toxicological perspectives. The basis of MCS is still to be identified, although a large number of hypersensitivity, immunological, psychological, neurological and toxicological mechanisms have been suggested, including: allergy; autosuggestion; cacosomia; conditioned response; immunological; impairment of biochemical pathways involved in energy production; impairment of neurochemical pathways; illness belief system; limbic kindling; olfactory threshold sensitivity; panic disorder; psychosomatic condition; malingering; neurogenic inflammation; overload of biotransformation pathways (also linked with free radical production); psychological or psychiatric illness; airway reactivity; sensitisation of the neurological system; time dependent sensitisation, toxicant induced loss of tolerance. Most of these theories tend to break down into concepts involving: (1) disruption in immunological/allergy processes; (2) alteration in nervous system function; (3) changes in biochemical or biotransformation capacity; (4) changes in psychological/neurobehavioural function. Research into the possible mechanisms of MCS is far from complete. However, a number of promising avenues of investigation indicate that the possibility of alteration of the sensitivity of nervous system cells (neurogenic inflammation, limbic kindling, cacosomia, neurogenic switching) are a possible mechanism for MCS.

  1. A Rapid Compression Expansion Machine (RCEM) for studying chemical kinetics: Experimental principle and first applications

    CERN Document Server

    Werler, Marc; Maas, Ulrich

    2016-01-01

    A novel extension of a rapid compression machine (RCM), namely a Rapid Compression Expansion Machine (RCEM), is described and its use for studying chemical kinetics is demonstrated. Like conventional RCMs, the RCEM quickly compresses a fuel/air mixture by pushing a piston into a cylinder; the resulting high temperatures and pressures initiate chemical reactions. In addition, the machine can rapidly expand the compressed gas in a controlled way by pulling the piston outwards again. This freezes chemical activity after a pre-defined reaction duration, and therefore allows a convenient probe sampling and ex-situ gas analysis of stable species. The RCEM therefore is a promising instrument for studying chemical kinetics, including also partially reacted fuel/air mixtures. The setup of the RCEM, its experimental characteristics and its use for studying chemical reactions are outlined in detail. To allow comparisons of RCEM results with predictions of chemical reaction mechanisms, a simple numerical model of the RCE...

  2. Development of chemical kinetic models for lean NOx traps.

    Energy Technology Data Exchange (ETDEWEB)

    Larson, Richard S.

    2010-04-01

    Overall project goal: Obtain the fundamental surface chemistry knowledge needed for the design and optimal utilization of NOx trap catalysts, thereby helping to speed the widespread adoption of this technology. Relevance to VT Program goals: Effective, durable advanced aftertreatment systems for lean-burn engines must be available if the fuel economy advantages of these engines are to be realized. Specific current year objective: Identify and correct any deficiencies in the previously developed reaction mechanism describing normal storage/regeneration cycles, and complete development of a supplementary mechanism accounting for the effects of sulfation. A fundamental understanding of LNT chemistry is needed to realize the full potential of this aftertreatment technology, which could lead to greater use of fuel-efficient lean-burn engines. We have used a multi-tiered approach to developing an elementary chemical mechanism benchmarked against experimental data: (1) Simulate a set of steady flow experiments, with storage effects minimized, to infer a tentative mechanism for chemistry on precious metal sites (completed). (2) Simulate a set of long cycle experiments to infer a mechanism for NOx and oxygen storage sites while simultaneously finalizing precious metal chemistry (completed). (3) Simulate a simplified sulfation/desulfation protocol to obtain a supplementary set of reactions involving sulfur on all three kinds of sites (nearly completed). (4) Investigate the potential role of reductants other than CO and H{sub 2}. While simulation of isothermal experiments is the preferred way to extract kinetic parameters, simulation of realistic storage/regeneration cycles requires that exotherms be considered. Our ultimate goal is to facilitate improved designs for LNT-based aftertreatment systems and to assist in the development of improved catalysts.

  3. The applications of chemical thermodynamics and chemical kinetics to planetary atmospheres research

    Science.gov (United States)

    Fegley, Bruce, Jr.

    1990-01-01

    A review of the applications of chemical thermodynamics and chemical kinetics to planetary atmospheres research during the past four decades is presented with an emphasis on chemical equilibrium models and thermochemical kinetics. Several current problems in planetary atmospheres research such as the origin of the atmospheres of the terrestrial planets, atmosphere-surface interactions on Venus and Mars, deep mixing in the atmospheres of the gas giant planets, and the origin of the atmospheres of outer planet satellites all require laboratory data on the kinetics of thermochemical reactions for their solution.

  4. Mean-field cooperativity in chemical kinetics

    OpenAIRE

    Di Biasio, Aldo; Agliari, Elena; Barra, Adriano; Burioni, Raffaella

    2011-01-01

    We consider cooperative reactions and we study the effects of the interaction strength among the system components on the reaction rate, hence realizing a connection between microscopic and macroscopic observables. Our approach is based on statistical mechanics models and it is developed analytically via mean-field techniques. First of all, we show that, when the coupling strength is set positive, the model is able to consistently recover all the various cooperative measures previously introd...

  5. Reduced Models in Chemical Kinetics via Nonlinear Data-Mining

    Directory of Open Access Journals (Sweden)

    Eliodoro Chiavazzo

    2014-01-01

    Full Text Available The adoption of detailed mechanisms for chemical kinetics often poses two types of severe challenges: First, the number of degrees of freedom is large; and second, the dynamics is characterized by widely disparate time scales. As a result, reactive flow solvers with detailed chemistry often become intractable even for large clusters of CPUs, especially when dealing with direct numerical simulation (DNS of turbulent combustion problems. This has motivated the development of several techniques for reducing the complexity of such kinetics models, where, eventually, only a few variables are considered in the development of the simplified model. Unfortunately, no generally applicable a priori recipe for selecting suitable parameterizations of the reduced model is available, and the choice of slow variables often relies upon intuition and experience. We present an automated approach to this task, consisting of three main steps. First, the low dimensional manifold of slow motions is (approximately sampled by brief simulations of the detailed model, starting from a rich enough ensemble of admissible initial conditions. Second, a global parametrization of the manifold is obtained through the Diffusion Map (DMAP approach, which has recently emerged as a powerful tool in data analysis/machine learning. Finally, a simplified model is constructed and solved on the fly in terms of the above reduced (slow variables. Clearly, closing this latter model requires nontrivial interpolation calculations, enabling restriction (mapping from the full ambient space to the reduced one and lifting (mapping from the reduced space to the ambient one. This is a key step in our approach, and a variety of interpolation schemes are reported and compared. The scope of the proposed procedure is presented and discussed by means of an illustrative combustion example.

  6. Prospective Chemistry Teachers' Conceptions of Chemical Thermodynamics and Kinetics

    Science.gov (United States)

    Sozbilir, Mustafa; Pinarbasi, Tacettin; Canpolat, Nurtac

    2010-01-01

    This study aimed at identifying specifically prospective chemistry teachers' difficulties in determining the differences between the concepts of chemical thermodynamics and kinetics. Data were collected from 67 prospective chemistry teachers at Kazim Karabekir Education Faculty of Ataturk University in Turkey during 2005-2006 academic year. Data…

  7. Chemical Kinetics at the Single-Molecule Level

    Science.gov (United States)

    Levitus, Marcia

    2011-01-01

    For over a century, chemists have investigated the rates of chemical reactions using experimental conditions involving huge numbers of molecules. As a consequence, the description of the kinetics of the reaction in terms of average values was good enough for all practical purposes. From the pedagogical point of view, such a description misses the…

  8. Cleaner combustion developing detailed chemical kinetic models

    CERN Document Server

    Battin-Leclerc, Frédérique; Blurock, Edward

    2013-01-01

    This overview compiles the on-going research in Europe to enlarge and deepen the understanding of the reaction mechanisms and pathways associated with the combustion of an increased range of fuels. Focus is given to the formation of a large number of hazardous minor pollutants and the inability of current combustion models to predict the  formation of minor products such as alkenes, dienes, aromatics, aldehydes and soot nano-particles which have a deleterious impact on both the environment and on human health. Cleaner Combustion describes, at a fundamental level, the reactive chemistry of min

  9. Reactive molecular dynamics simulation and chemical kinetic modeling of pyrolysis and combustion of n-dodecane

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Quan-De [College of Chemistry, Sichuan University, Chengdu (China); Wang, Jing-Bo; Li, Juan-Qin; Tan, Ning-Xin; Li, Xiang-Yuan [College of Chemical Engineering, Sichuan University, Chengdu (China)

    2011-02-15

    The initiation mechanisms and kinetics of pyrolysis and combustion of n-dodecane are investigated by using the reactive molecular dynamics (ReaxFF MD) simulation and chemical kinetic modeling. From ReaxFF MD simulations, we find the initiation mechanisms of pyrolysis of n-dodecane are mainly through two pathways, (1) the cleavage of C-C bond to form smaller hydrocarbon radicals, and (2) the dehydrogenation reaction to form an H radical and the corresponding n-C{sub 12}H{sub 25} radical. Another pathway is the H-abstraction reactions by small radicals including H, CH{sub 3}, and C{sub 2}H{sub 5}, which are the products after the initiation reaction of n-dodecane pyrolysis. ReaxFF MD simulations lead to reasonable Arrhenius parameters compared with experimental results based on first-order kinetic analysis of n-dodecane pyrolysis. The density/pressure effects on the pyrolysis of n-dodecane are also analyzed. By appropriate mapping of the length and time from macroscopic kinetic modeling to ReaxFF MD, a simple comparison of the conversion of n-dodecane from ReaxFF MD simulations and that from kinetic modeling is performed. In addition, the oxidation of n-dodecane is studied by ReaxFF MD simulations. We find that formaldehyde molecule is an important intermediate in the oxidation of n-dodecane, which has been confirmed by kinetic modeling, and ReaxFF leads to reasonable reaction pathways for the oxidation of n-dodecane. These results indicate that ReaxFF MD simulations can give an atomistic description of the initiation mechanism and product distributions of pyrolysis and combustion for hydrocarbon fuels, and can be further used to provide molecular based robust kinetic reaction mechanism for chemical kinetic modeling of hydrocarbon fuels. (author)

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

    Science.gov (United States)

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

    1985-01-01

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

  11. Computer-Aided Construction of Chemical Kinetic Models

    Energy Technology Data Exchange (ETDEWEB)

    Green, William H. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

    2014-12-31

    The combustion chemistry of even simple fuels can be extremely complex, involving hundreds or thousands of kinetically significant species. The most reasonable way to deal with this complexity is to use a computer not only to numerically solve the kinetic model, but also to construct the kinetic model in the first place. Because these large models contain so many numerical parameters (e.g. rate coefficients, thermochemistry) one never has sufficient data to uniquely determine them all experimentally. Instead one must work in “predictive” mode, using theoretical rather than experimental values for many of the numbers in the model, and as appropriate refining the most sensitive numbers through experiments. Predictive chemical kinetics is exactly what is needed for computer-aided design of combustion systems based on proposed alternative fuels, particularly for early assessment of the value and viability of proposed new fuels before those fuels are commercially available. This project was aimed at making accurate predictive chemical kinetics practical; this is a challenging goal which requires a range of science advances. The project spanned a wide range from quantum chemical calculations on individual molecules and elementary-step reactions, through the development of improved rate/thermo calculation procedures, the creation of algorithms and software for constructing and solving kinetic simulations, the invention of methods for model-reduction while maintaining error control, and finally comparisons with experiment. Many of the parameters in the models were derived from quantum chemistry calculations, and the models were compared with experimental data measured in our lab or in collaboration with others.

  12. KINETICS AND MECHANISMS OF NOx - CHAR REDUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Suuberg, E.M.

    1998-06-19

    This study was undertaken in order to improve understanding of several aspects of the NO-carbon reaction. This reaction is of practical importance in combustion systems, but its close examination also provides some fundamental insight into oxidizing gas-carbon reactions. As part of this study, a comprehensive literature review of earlier work on this reaction has been published (Aarna and Suuberg, Fuel, 1997, 76, 475-491). It has been thought for some time that the kinetics of the NO-carbon reaction are unusual, in that they often show a two-regime Arrhenius behavior. It has, however, turned out during this work that NO is not alone in this regard. In this laboratory, we also uncovered evidence of two kinetic regime behavior in CO{sub 2} gasification. In another laboratory, a former colleague has identified the same behavior in N{sub 2}O. The low temperature reaction regime always shows an activation energy which is lower than that in the high temperature regime, leaving little doubt that a shift in mechanism, as opposed to transport limitations, dictates the behavior. The activation energy of the low temperature regime of these reactions is typically less than 100 kJ/mol, and the activation energy of the high temperature regime is generally considerably in excess of this value. In this study, we have resolved some apparent inconsistencies in the explanation of the low temperature regime, whose rate has generally been ascribed to desorption-controlled processes. Part of the problem in characterization of the different temperature regimes is that they overlap to a high degree. It is difficult to probe the low temperature regime experimentally, because of slow relaxation of the surface oxides in that regime. Using careful experimental techniques, we were able to demonstrate that the low temperature regime is indeed characterized by zero order in NO, as it must be. A separate study is being carried out to model the behavior in this regime in NO and in other gases, and

  13. Infrared absorption spectroscopy and chemical kinetics of free radicals

    Energy Technology Data Exchange (ETDEWEB)

    Curl, R.F.; Glass, G.P. [Rice Univ., Houston, TX (United States)

    1993-12-01

    This research is directed at the detection, monitoring, and study of chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. During the last year, infrared kinetic spectroscopy using excimer laser flash photolysis and color-center laser probing has been employed to study the high resolution spectrum of HCCN, the rate constant of the reaction between ethynyl (C{sub 2}H) radical and H{sub 2} in the temperature region between 295 and 875 K, and the recombination rate of propargyl (CH{sub 2}CCH) at room temperature.

  14. Fast algorithm for calculating chemical kinetics in turbulent reacting flow

    International Nuclear Information System (INIS)

    The design of a very fast, automatic black-box code for homogeneous, gas-phase chemical kinetics problems requires an understanding of the physical and numerical sources of computational inefficiency. Some major sources reviewed in this paper are stiffness of the governing ordinary differential equations and its detection, choice of appropriate method (i.e., integration algorithm plus stepsize control strategy), nonphysical initial conditions, and too frequent evaluation of thermochemical and kinetic properties. Specific techniques are recommended (and some advised against) for improving or overcoming the identified problem areas. It is argued that, because reactive species increase exponentially with time during induction and early heat release, and all species exhibit asymptotic, exponential decay with time during late heat release and equilibration, exponential-fitted integration algorithms are inherently more accurate for kinetics modeling than classical, polynomial-interpolant methods for the same computational work

  15. Chemical Mechanism Solvers in Air Quality Models

    OpenAIRE

    Linford, John C.; Adrian Sandu; Rolf Sander; Hong Zhang

    2011-01-01

    The solution of chemical kinetics is one of the most computationally intensive tasks in atmospheric chemical transport simulations. Due to the stiff nature of the system, implicit time stepping algorithms which repeatedly solve linear systems of equations are necessary. This paper reviews the issues and challenges associated with the construction of efficient chemical solvers, discusses several families of algorithms, presents strategies for increasing computational efficiency, and gives insi...

  16. Nonlinear Stochastic Dynamics of Complex Systems, I: A Chemical Reaction Kinetic Perspective with Mesoscopic Nonequilibrium Thermodynamics

    CERN Document Server

    Qian, Hong

    2016-01-01

    We distinguish a mechanical representation of the world in terms of point masses with positions and momenta and the chemical representation of the world in terms of populations of different individuals, each with intrinsic stochasticity, but population wise with statistical rate laws in their syntheses, degradations, spatial diffusion, individual state transitions, and interactions. Such a formal kinetic system in a small volume $V$, like a single cell, can be rigorously treated in terms of a Markov process describing its nonlinear kinetics as well as nonequilibrium thermodynamics at a mesoscopic scale. We introduce notions such as open, driven chemical systems, entropy production, free energy dissipation, etc. Then in the macroscopic limit, we illustrate how two new "laws", in terms of a generalized free energy of the mesoscopic stochastic dynamics, emerge. Detailed balance and complex balance are two special classes of "simple" nonlinear kinetics. Phase transition is intrinsically related to multi-stability...

  17. Mesoscopic Kinetic Basis of Macroscopic Chemical Thermodynamics: A Mathematical Theory

    CERN Document Server

    Ge, Hao

    2016-01-01

    From a mathematical model that describes a complex chemical kinetic system of $N$ species and $M$ elementrary reactions in a rapidly stirred vessel of size $V$ as a Markov process, we show that a macroscopic chemical thermodynamics emerges as $V\\rightarrow\\infty$. The theory is applicable to linear and nonlinear reactions, closed systems reaching chemical equilibrium, or open, driven systems approaching to nonequilibrium steady states. A generalized mesoscopic free energy gives rise to a macroscopic chemical energy function $\\varphi^{ss}(\\vx)$ where $\\vx=(x_1,\\cdots,x_N)$ are the concentrations of the $N$ chemical species. The macroscopic chemical dynamics $\\vx(t)$ satisfies two emergent laws: (1) $(\\rd/\\rd t)\\varphi^{ss}[\\vx(t)]\\le 0$, and (2)$(\\rd/\\rd t)\\varphi^{ss}[\\vx(t)]=\\text{cmf}(\\vx)-\\sigma(\\vx)$ where entropy production rate $\\sigma\\ge 0$ represents the sink for the chemical energy, and chemical motive force $\\text{cmf}\\ge 0$ is non-zero if the system is driven under a sustained nonequilibrium chemos...

  18. The mechanism and kinetics of epoxy-amine reactions

    International Nuclear Information System (INIS)

    Full text.Silane coupling agents have an important role at the interface for improving the performance of composite materials based on polymer matrices reinforced with glass fibers or mineral fillers. The silanes are also used in some adhesive formulations or as substrate primers, giving higher strength of adhesives joints. In these interface or interphase problems, most of the data in the literature concerns the final properties of the composite materials, such as strength or young's modulus; there is very little information about the chemical properties of the interphase. The aim of this study is to try to provide some of this basic data. The coupling agent studied here is the γ-aminopropyltriethoxysilane (γ-APS) or A1100. It is the most commonly used coupling agents. During composite processing, it is frequently reacted with an epoxy prepolymer based on diglycidylether of bisphenol A. We have studied these reactions from a fundamental point of view and not in industrial conditions. First we compared the kinetics results of different analytical techniques. Secondly, we compared the reactivities of the epoxy in DGEBA and the amino-hydrogen functions in coupling agent to those of model reagents like phenylglycidylether and hexylamine. the third part consists of validating a kinetic mechanism and calculating the rate constants, activation energy and reactivity ratios

  19. 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.

  20. Reduced and Validated Kinetic Mechanisms for Hydrogen-CO-sir Combustion in Gas Turbines

    Energy Technology Data Exchange (ETDEWEB)

    Yiguang Ju; Frederick Dryer

    2009-02-07

    Rigorous experimental, theoretical, and numerical investigation of various issues relevant to the development of reduced, validated kinetic mechanisms for synthetic gas combustion in gas turbines was carried out - including the construction of new radiation models for combusting flows, improvement of flame speed measurement techniques, measurements and chemical kinetic analysis of H{sub 2}/CO/CO{sub 2}/O{sub 2}/diluent mixtures, revision of the H{sub 2}/O{sub 2} kinetic model to improve flame speed prediction capabilities, and development of a multi-time scale algorithm to improve computational efficiency in reacting flow simulations.

  1. Kinetics and mechanism of synthetic CoS oxidation process

    Directory of Open Access Journals (Sweden)

    Štrbac N.

    2006-01-01

    Full Text Available The results of investigation of kinetics and mechanism for synthetic a-CoS oxidation process are presented in this paper. Based on experimental data obtained using DTA and XRD analysis and constructed PSD diagrams for Co-S-O system, mechanism of synthetic a-CoS oxidation process is suggested. Characteristic kinetic parameters were obtained for experimental isothermal investigations of desulfurization degree using Sharp method.

  2. Chemical Kinetic Study of Nitrogen Oxides Formation Trends in Biodiesel Combustion

    OpenAIRE

    Junfeng Yang; Valeri I. Golovitchev; Pau Redón Lurbe; J. Javier López Sánchez

    2012-01-01

    The use of biodiesel in conventional diesel engines results in increased NOx emissions; this presents a barrier to the widespread use of biodiesel. The origins of this phenomenon were investigated using the chemical kinetics simulation tool: CHEMKIN-2 and the CFD KIVA3V code, which was modified to account for the physical properties of biodiesel and to incorporate semidetailed mechanisms for its combustion and the formation of emissions. Parametric ϕ-T maps and 3D engine simulations were used...

  3. Progress in Chemical Kinetic Modeling for Surrogate Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Pitz, W J; Westbrook, C K; Herbinet, O; Silke, E J

    2008-06-06

    Gasoline, diesel, and other alternative transportation fuels contain hundreds to thousands of compounds. It is currently not possible to represent all these compounds in detailed chemical kinetic models. Instead, these fuels are represented by surrogate fuel models which contain a limited number of representative compounds. We have been extending the list of compounds for detailed chemical models that are available for use in fuel surrogate models. Detailed models for components with larger and more complicated fuel molecular structures are now available. These advancements are allowing a more accurate representation of practical and alternative fuels. We have developed detailed chemical kinetic models for fuels with higher molecular weight fuel molecules such as n-hexadecane (C16). Also, we can consider more complicated fuel molecular structures like cyclic alkanes and aromatics that are found in practical fuels. For alternative fuels, the capability to model large biodiesel fuels that have ester structures is becoming available. These newly addressed cyclic and ester structures in fuels profoundly affect the reaction rate of the fuel predicted by the model. Finally, these surrogate fuel models contain large numbers of species and reactions and must be reduced for use in multi-dimensional models for spark-ignition, HCCI and diesel engines.

  4. EFFECTIVE SOLUTION METHOD OF CHEMICAL REACTION KINETICS WITH DIFFUSE

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    The time integration method with four-order accuracy, self-starting and implicit for the diffuse chemical reaction kinetics equation or the transient instantaneous temperature filed equation was presented. The examples show that both accuracy and stability are better than Runge-Kutta method with four-order. The coefficients of the equation are stored with sparse matrix pattern, so an algorithm is presented which combines a compact storage scheme with reduced computation cost. The computation of the competitive and consecutive reaction in the rotating packed bed, taken as examples,shows that the method is effective.

  5. Large deviations for two scale chemical kinetic processes

    CERN Document Server

    Li, Tiejun

    2015-01-01

    We formulate the large deviations for a class of two scale chemical kinetic processes motivated from biological applications. The result is successfully applied to treat a genetic switching model with positive feedbacks. The corresponding Hamiltonian is convex with respect to the momentum variable as a by-product of the large deviation theory. This property ensures its superiority in the rare event simulations compared with the result obtained by formal WKB asymptotics. The result is of general interest to understand the large deviations for multiscale problems.

  6. Chemical kinetic simulation of kerosene combustion in an individual flame tube

    Directory of Open Access Journals (Sweden)

    Wen Zeng

    2014-05-01

    Full Text Available The use of detailed chemical reaction mechanisms of kerosene is still very limited in analyzing the combustion process in the combustion chamber of the aircraft engine. In this work, a new reduced chemical kinetic mechanism for fuel n-decane, which selected as a surrogate fuel for kerosene, containing 210 elemental reactions (including 92 reversible reactions and 26 irreversible reactions and 50 species was developed, and the ignition and combustion characteristics of this fuel in both shock tube and flat-flame burner were kinetic simulated using this reduced reaction mechanism. Moreover, the computed results were validated by experimental data. The calculated values of ignition delay times at pressures of 12, 50 bar and equivalence ratio is 1.0, 2.0, respectively, and the main reactants and main products mole fractions using this reduced reaction mechanism agree well with experimental data. The combustion processes in the individual flame tube of a heavy duty gas turbine combustor were simulated by coupling this reduced reaction mechanism of surrogate fuel n-decane and one step reaction mechanism of surrogate fuel C12H23 into the computational fluid dynamics software. It was found that this reduced reaction mechanism is shown clear advantages in simulating the ignition and combustion processes in the individual flame tube over the one step reaction mechanism.

  7. An Experimental and Chemical Kinetics Study of the Combustion of Syngas and High Hydrogen Content Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Santoro, Robers [Pennsylvania State Univ., State College, PA (United States); Dryer, Frederick [Princeton Univ., NJ (United States); Ju, Yiguang [Princeton Univ., NJ (United States)

    2013-09-30

    An integrated and collaborative effort involving experiments and complementary chemical kinetic modeling investigated the effects of significant concentrations of water and CO2 and minor contaminant species (methane [CH4], ethane [C2H6], NOX, etc.) on the ignition and combustion of HHC fuels. The research effort specifically addressed broadening the experimental data base for ignition delay, burning rate, and oxidation kinetics at high pressures, and further refinement of chemical kinetic models so as to develop compositional specifications related to the above major and minor species. The foundation for the chemical kinetic modeling was the well validated mechanism for hydrogen and carbon monoxide developed over the last 25 years by Professor Frederick Dryer and his co-workers at Princeton University. This research furthered advance the understanding needed to develop practical guidelines for realistic composition limits and operating characteristics for HHC fuels. A suite of experiments was utilized that that involved a high-pressure laminar flow reactor, a pressure-release type high-pressure combustion chamber and a high-pressure turbulent flow reactor.

  8. Incorporation of chemical kinetic models into process control

    International Nuclear Information System (INIS)

    An important consideration in chemical process control is to determine the precise rationing of reactant streams, particularly when a large time delay exists between the mixing of the reactants and the measurement of the product. In this paper, a method is described for incorporating chemical kinetic models into the control strategy in order to achieve optimum operating conditions. The system is first characterized by determining a reaction rate surface as a function of all input reactant concentrations over a feasible range. A nonlinear constrained optimization program is then used to determine the combination of reactants which produces the specified yield at minimum cost. This operating condition is then used to establish the nominal concentrations of the reactants. The actual operation is determined through a feedback control system employing a Smith predictor. The method is demonstrated on a laboratory bench scale enzyme reactor

  9. Uncovering Oscillations, Complexity, and Chaos in Chemical Kinetics Using Mathematica

    Science.gov (United States)

    Ferreira, M. M. C.; Ferreira, W. C., Jr.; Lino, A. C. S.; Porto, M. E. G.

    1999-06-01

    Unlike reactions with no peculiar temporal behavior, in oscillatory reactions concentrations can rise and fall spontaneously in a cyclic or disorganized fashion. In this article, the software Mathematica is used for a theoretical study of kinetic mechanisms of oscillating and chaotic reactions. A first simple example is introduced through a three-step reaction, called the Lotka model, which exhibits a temporal behavior characterized by damped oscillations. The phase plane method of dynamic systems theory is introduced for a geometric interpretation of the reaction kinetics without solving the differential rate equations. The equations are later numerically solved using the built-in routine NDSolve and the results are plotted. The next example, still with a very simple mechanism, is the Lotka-Volterra model reaction, which oscillates indefinitely. The kinetic process and rate equations are also represented by a three-step reaction mechanism. The most important difference between this and the former reaction is that the undamped oscillation has two autocatalytic steps instead of one. The periods of oscillations are obtained by using the discrete Fourier transform (DFT)-a well-known tool in spectroscopy, although not so common in this context. In the last section, it is shown how a simple model of biochemical interactions can be useful to understand the complex behavior of important biological systems. The model consists of two allosteric enzymes coupled in series and activated by its own products. This reaction scheme is important for explaining many metabolic mechanisms, such as the glycolytic oscillations in muscles, yeast glycolysis, and the periodic synthesis of cyclic AMP. A few of many possible dynamic behaviors are exemplified through a prototype glycolytic enzymatic reaction proposed by Decroly and Goldbeter. By simply modifying the initial concentrations, limit cycles, chaos, and birhythmicity are computationally obtained and visualized.

  10. Nitrile reaction in high-temperature water: Kinetics and mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Izzo, B.; Harrell, C.L.; Klein, M.T. [Univ. of Delaware, Newark, DE (United States). Dept. of Chemical Engineering

    1997-08-01

    The reaction pathways, kinetics and mechanisms underlying the hydrolysis of aliphatic and aromatic nitriles in high-temperature water (HTW) were investigated. The reaction products were the associated amides and carboxylic acids. Autocatalytic kinetics were observed and confirmed by experiment and analysis of the physical chemistry of the HTW reaction environment. A model incorporating two autocatalytic steps captured the observed kinetics well, and the associated optimized rate constants highlighted the key differences in the reaction chemistry of aliphatic and aromatic nitriles. The rate behavior of nitrile hydrolysis at these conditions has tangible consequences regarding optimal processing strategies.

  11. Investigation of Chemical Kinetics on Soot Formation Event of n-Heptane Spray Combustion

    DEFF Research Database (Denmark)

    Pang, Kar Mun; Jangi, Mehdi; Bai, Xue-Song;

    2014-01-01

    In this reported work, 2-dimsensional computational fluid dynamics studies of n-heptane combustion and soot formation processes in the Sandia constant-volume vessel are carried out. The key interest here is to elucidate how the chemical kinetics affects the combustion and soot formation events....... Numerical computation is performed using OpenFOAM and chemistry coordinate mapping (CCM) approach is used to expedite the calculation. Three n-heptane kinetic mechanisms with different chemistry sizes and comprehensiveness in oxidation pathways and soot precursor formation are adopted. The three examined...... chemical models use acetylene (C2H2), benzene ring (A1) and pyrene (A4) as soot precursor. They are henceforth addressed as nhepC2H2, nhepA1 and nhepA4, respectively for brevity. Here, a multistep soot model is coupled with the spray combustion solver to simulate the soot formation/oxidation processes...

  12. Accelerating moderately stiff chemical kinetics in reactive-flow simulations using GPUs

    CERN Document Server

    Niemeyer, Kyle E

    2014-01-01

    The chemical kinetics ODEs arising from operator-split reactive-flow simulations were solved on GPUs using explicit integration algorithms. Nonstiff chemical kinetics of a hydrogen oxidation mechanism (9 species and 38 irreversible reactions) were computed using the explicit fifth-order Runge-Kutta-Cash-Karp method, and the GPU-accelerated version performed faster than single- and six-core CPU versions by factors of 126 and 25, respectively, for 524,288 ODEs. Moderately stiff kinetics, represented with mechanisms for hydrogen/carbon-monoxide (13 species and 54 irreversible reactions) and methane (53 species and 634 irreversible reactions) oxidation, were computed using the stabilized explicit second-order Runge-Kutta-Chebyshev (RKC) algorithm. The GPU-based RKC implementation demonstrated an increase in performance of nearly 59 and 10 times, for problem sizes consisting of 262,144 ODEs and larger, than the single- and six-core CPU-based RKC algorithms using the hydrogen/carbon-monoxide mechanism. With the met...

  13. Parameter Optimization of Nitriding Process Using Chemical Kinetics

    Science.gov (United States)

    Özdemir, İ. Bedii; Akar, Firat; Lippmann, Nils

    2016-09-01

    Using the dynamics of chemical kinetics, an investigation to search for an optimum condition for a gas nitriding process is performed over the solution space spanned by the initial temperature and gas composition of the furnace. For a two-component furnace atmosphere, the results are presented in temporal variations of gas concentrations and the nitrogen coverage on the surface. It seems that the exploitation of the nitriding kinetics can provide important feedback for setting the model-based control algorithms. The present work shows that when the nitrogen gas concentration is not allowed to exceed 6 pct, the Nad coverage can attain maximum values as high as 0.97. The time evolution of the Nad coverage also reveals that, as long as the temperature is above the value where nitrogen poisoning of the surface due to the low-temperature adsorption of excess nitrogen occurs, the initial ammonia content in the furnace atmosphere is much more important in the nitriding process than is the initial temperature.

  14. An open-source chemical kinetics network: VULCAN

    Science.gov (United States)

    Tsai, Shang-Min; Lyons, James; Heng, Kevin

    2015-12-01

    I will present VULCAN, an open-source 1D chemical kinetics code suited for the temperature and pressure range relevant to observable exoplanet atmospheres. The chemical network is based on a set of reduced rate coefficients for C-H-O systems. Most of the rate coefficients are based on the NIST online database, and validated by comparing withthermodynamic equilibrium codes (TEA, STANJAN). The difference between the experimental rates and those from the thermodynamical data is carefully examined and discussed. For the numerical method, a simple, quick, semi-implicit Euler integrator is adopted to solve the stiff chemical reactions, within an operator-splitting scheme for computational efficiency.Several test runs of VULCAN are shown in a hierarchical way: pure H, H+O, H+O+C, including controlled experiments performed with a simple analytical temperature-pressure profiles, so that different parameters, such as the stellar irradiation, atmospheric opacities and albedo can be individually explored to understand how these properties affect the temperaturestructure and hence the chemical abundances. I will also revisit the "transport-induced-quenching” effects, and discuss the limitation of this approximation and its impact on observations. Finally, I will discuss the effects of C/O ratio and compare with published work in the literature.VULCAN is written in Python and is part of the publicly-available set of community tools we call the Exoclimes Simulation Platform (ESP; www.exoclime.org). I am a Ph.D student of Kevin Heng at the University of Bern, Switzerland.

  15. Gompertz kinetics model of fast chemical neurotransmission currents.

    Science.gov (United States)

    Easton, Dexter M

    2005-10-01

    At a chemical synapse, transmitter molecules ejected from presynaptic terminal(s) bind reversibly with postsynaptic receptors and trigger an increase in channel conductance to specific ions. This paper describes a simple but accurate predictive model for the time course of the synaptic conductance transient, based on Gompertz kinetics. In the model, two simple exponential decay terms set the rates of development and decline of transmitter action. The first, r, triggering conductance activation, is surrogate for the decelerated rate of growth of conductance, G. The second, r', responsible for Y, deactivation of the conductance, is surrogate for the decelerated rate of decline of transmitter action. Therefore, the differential equation for the net conductance change, g, triggered by the transmitter is dg/dt=g(r-r'). The solution of that equation yields the product of G(t), representing activation, and Y(t), which defines the proportional decline (deactivation) of the current. The model fits, over their full-time course, published records of macroscopic ionic current associated with fast chemical transmission. The Gompertz model is a convenient and accurate method for routine analysis and comparison of records of synaptic current and putative transmitter time course. A Gompertz fit requiring only three independent rate constants plus initial current appears indistinguishable from a Markov fit using seven rate constants.

  16. Chemical Kinetics in Support of Syngas Turbine Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Dryer, Frederick

    2007-07-31

    This document is the final report on an overall program formulated to extend our prior work in developing and validating kinetic models for the CO/hydrogen/oxygen reaction by carefully analyzing the individual and interactive behavior of specific elementary and subsets of elementary reactions at conditions of interest to syngas combustion in gas turbines. A summary of the tasks performed under this work are: 1. Determine experimentally the third body efficiencies in H+O{sub 2}+M = HO{sub 2}+M (R1) for CO{sub 2} and H{sub 2}O. 2. Using published literature data and the results in this program, further develop the present H{sub 2}/O{sub 2}/diluent and CO/H{sub 2}/O{sub 2}/diluent mechanisms for dilution with CO{sub 2}, H{sub 2}O and N{sub 2} through comparisons with new experimental validation targets for H{sub 2}-CO-O{sub 2}-N{sub 2} reaction kinetics in the presence of significant diluent fractions of CO{sub 2} and/or H{sub 2}O, at high pressures. (task amplified to especially address ignition delay issues, see below). 3. Analyze and demonstrate issues related to NOx interactions with syngas combustion chemistry (task amplified to include interactions of iron pentacarbonyl with syngas combustion chemistry, see below). 4. Publish results, including updated syngas kinetic model. Results are summarized in this document and its appendices. Three archival papers which contain a majority of the research results have appeared. Those results not published elsewhere are highlighted here, and will appear as part of future publications. Portions of the work appearing in the above publications were also supported in part by the Department of Energy under Grant No. DE-FG02-86ER-13503. As a result of and during the research under the present contract, we became aware of other reported results that revealed substantial differences between experimental characterizations of ignition delays for syngas mixtures and ignition delay predictions based upon homogenous kinetic modeling. We

  17. Modeling turbulence structure. Chemical kinetics interaction in turbulent reactive flows

    Energy Technology Data Exchange (ETDEWEB)

    Magnussen, B.F. [The Norwegian Univ. of Science and Technology, Trondheim (Norway)

    1997-12-31

    The challenge of the mathematical modelling is to transfer basic physical knowledge into a mathematical formulation such that this knowledge can be utilized in computational simulation of practical problems. The combustion phenomena can be subdivided into a large set of interconnected phenomena like flow, turbulence, thermodynamics, chemical kinetics, radiation, extinction, ignition etc. Combustion in one application differs from combustion in another area by the relative importance of the various phenomena. The difference in fuel, geometry and operational conditions often causes the differences. The computer offers the opportunity to treat the individual phenomena and their interactions by models with wide operational domains. The relative magnitude of the various phenomena therefore becomes the consequence of operational conditions and geometry and need not to be specified on the basis of experience for the given problem. In mathematical modelling of turbulent combustion, one of the big challenges is how to treat the interaction between the chemical reactions and the fluid flow i.e. the turbulence. Different scientists adhere to different concepts like the laminar flamelet approach, the pdf approach of the Eddy Dissipation Concept. Each of these approaches offers different opportunities and problems. All these models are based on a sound physical basis, however none of these have general validity in taking into consideration all detail of the physical chemical interaction. The merits of the models can only be judged by their ability to reproduce physical reality and consequences of operational and geometric conditions in a combustion system. The presentation demonstrates and discusses the development of a coherent combustion technology for energy conversion and safety based on the Eddy Dissipation Concept by Magnussen. (author) 30 refs.

  18. Upper D region chemical kinetic modeling of LORE relaxation times

    Science.gov (United States)

    Gordillo-Vázquez, F. J.; Luque, A.; Haldoupis, C.

    2016-04-01

    The recovery times of upper D region electron density elevations, caused by lightning-induced electromagnetic pulses (EMP), are modeled. The work was motivated from the need to understand a recently identified narrowband VLF perturbation named LOREs, an acronym for LOng Recovery Early VLF events. LOREs associate with long-living electron density perturbations in the upper D region ionosphere; they are generated by strong EMP radiated from large peak current intensities of ±CG (cloud to ground) lightning discharges, known also to be capable of producing elves. Relaxation model scenarios are considered first for a weak enhancement in electron density and then for a much stronger one caused by an intense lightning EMP acting as an impulsive ionization source. The full nonequilibrium kinetic modeling of the perturbed mesosphere in the 76 to 92 km range during LORE-occurring conditions predicts that the electron density relaxation time is controlled by electron attachment at lower altitudes, whereas above 79 km attachment is balanced totally by associative electron detachment so that electron loss at these higher altitudes is controlled mainly by electron recombination with hydrated positive clusters H+(H2O)n and secondarily by dissociative recombination with NO+ ions, a process which gradually dominates at altitudes >88 km. The calculated recovery times agree fairly well with LORE observations. In addition, a simplified (quasi-analytic) model build for the key charged species and chemical reactions is applied, which arrives at similar results with those of the full kinetic model. Finally, the modeled recovery estimates for lower altitudes, that is <79 km, are in good agreement with the observed short recovery times of typical early VLF events, which are known to be associated with sprites.

  19. New directions: Atmospheric chemical mechanisms for the future

    Science.gov (United States)

    Kaduwela, Ajith; Luecken, Deborah; Carter, William; Derwent, Richard

    2015-12-01

    The atmospheric chemical reaction scheme, commonly referred to as the chemical mechanism, is the portion of an air quality model that represents the atmospheric chemistry of the pollutants. It is at the heart of every air quality model used in research and policy applications to predict and analyse the complex air pollutants: ozone, air toxics and PM2.5. The chemical mechanism should incorporate available information on chemical kinetics and reaction pathways and be the conduit through which the fundamental science of atmospheric chemistry is applied to solve real-world problems. The efficiency and effectiveness of policies developed to reduce exposure to harmful pollutants depend on how well the mechanisms reflect the actual chemistry. If the mechanism has reaction pathways that are incorrectly characterised or completely missing, the resulting predictions may underestimate emission reduction requirements needed to meet public health and ecosystem protection targets, or may overstate the emission reductions needed and cause unnecessary implementation costs. It is therefore essential that mechanisms utilise the best, most up-to-date atmospheric chemistry information available so that policy development is based on air quality model predictions that are robust, transparent and free from scientific challenge. We are concerned that this may not continue to be the case.

  20. Enzymatic hydrolysis of protein:mechanism and kinetic model

    Institute of Scientific and Technical Information of China (English)

    Qi Wei; He Zhimin

    2006-01-01

    The bioreaction mechanism and kinetic behavior of protein enzymatic hydrolysis for preparing active peptides were investigated to model and characterize the enzymatic hydrolysis curves.Taking into account single-substrate hydrolysis,enzyme inactivation and substrate or product inhibition,the reaction mechanism could be deduced from a series of experimental results carried out in a stirred tank reactor at different substrate concentrations,enzyme concentrations and temperatures based on M-M equation.An exponential equation dh/dt = aexp(-bh) was also established,where parameters a and b have different expressions according to different reaction mechanisms,and different values for different reaction systems.For BSA-trypsin model system,the regressive results agree with the experimental data,i.e.the average relative error was only 4.73%,and the reaction constants were determined as Km = 0.0748 g/L,Ks = 7.961 g/L,kd = 9.358/min,k2 =38.439/min,Ea= 64.826 kJ/mol,Ed= 80.031 kJ/mol in accordance with the proposed kinetic mode.The whole set of exponential kinetic equations can be used to model the bioreaction process of protein enzymatic hydrolysis,to calculate the thermodynamic and kinetic constants,and to optimize the operating parameters for bioreactor design.

  1. A Review of Research on the Teaching and Learning of Chemical Kinetics

    Science.gov (United States)

    Bain, Kinsey; Towns, Marcy H.

    2016-01-01

    We review literature on the teaching and learning of chemical kinetics at both the secondary and tertiary levels. Our aim in doing so is to summarize research literature, synthesize recommendations for future research, and suggest implications for practitioners. Two main bodies of literature emerged from the chemical kinetics education research:…

  2. Identifying Alternative Conceptions of Chemical Kinetics among Secondary School and Undergraduate Students in Turkey

    Science.gov (United States)

    Cakmakci, Gultekin

    2010-01-01

    This study identifies some alternative conceptions of chemical kinetics held by secondary school and undergraduate students (N = 191) in Turkey. Undergraduate students who participated are studying to become chemistry teachers when they graduate. Students' conceptions about chemical kinetics were elicited through a series of written tasks and…

  3. KinChem: A Computational Resource for Teaching and Learning Chemical Kinetics

    Science.gov (United States)

    da Silva, Jose´ Nunes, Jr.; Sousa Lima, Mary Anne; Silva Sousa, Eduardo Henrique; Oliveira Alexandre, Francisco Serra; Melo Leite, Antonio Jose´, Jr.

    2014-01-01

    This paper presents a piece of educational software covering a comprehensive number of topics of chemical kinetics, which is available free of charge in Portuguese and English. The software was developed to support chemistry educators and students in the teaching-learning process of chemical kinetics by using animations, calculations, and…

  4. Preservice Science Teachers' Attitudes towards Chemistry and Misconceptions about Chemical Kinetics

    Science.gov (United States)

    Çam, Aylin; Topçu, Mustafa Sami; Sülün, Yusuf

    2015-01-01

    The present study investigates preservice science teachers' attitudes towards chemistry; their misconceptions about chemical kinetics; and relationships between pre-service science teachers' attitudes toward chemistry and misconceptions about chemical kinetics were examined. The sample of this study consisted of 81 freshman pre-service science…

  5. Fourth-Order Vibrational Transition State Theory and Chemical Kinetics

    Science.gov (United States)

    Stanton, John F.; Matthews, Devin A.; Gong, Justin Z.

    2015-06-01

    Second-order vibrational perturbation theory (VPT2) is an enormously successful and well-established theory for treating anharmonic effects on the vibrational levels of semi-rigid molecules. Partially as a consequence of the fact that the theory is exact for the Morse potential (which provides an appropriate qualitative model for stretching anharmonicity), VPT2 calculations for such systems with appropriate ab initio potential functions tend to give fundamental and overtone levels that fall within a handful of wavenumbers of experimentally measured positions. As a consequence, the next non-vanishing level of perturbation theory -- VPT4 -- offers only slight improvements over VPT2 and is not practical for most calculations since it requires information about force constants up through sextic. However, VPT4 (as well as VPT2) can be used for other applications such as the next vibrational correction to rotational constants (the ``gammas'') and other spectroscopic parameters. In addition, the marriage of VPT with the semi-classical transition state theory of Miller (SCTST) has recently proven to be a powerful and accurate treatment for chemical kinetics. In this talk, VPT4-based SCTST tunneling probabilities and cumulative reaction probabilities are give for the first time for selected low-dimensional model systems. The prospects for VPT4, both practical and intrinsic, will also be discussed.

  6. Integration Strategies for Efficient Multizone Chemical Kinetics Models

    Energy Technology Data Exchange (ETDEWEB)

    McNenly, M J; Havstad, M A; Aceves, S M; Pitz, W J

    2009-10-15

    Three integration strategies are developed and tested for the stiff, ordinary differential equation (ODE) integrators used to solve the fully coupled multizone chemical kinetics model. Two of the strategies tested are found to provide more than an order of magnitude of improvement over the original, basic level of usage for the stiff ODE solver. One of the faster strategies uses a decoupled, or segregated, multizone model to generate an approximate Jacobian. This approach yields a 35-fold reduction in the computational cost for a 20 zone model. Using the same approximate Jacobian as a preconditioner for an iterative Krylov-type linear system solver, the second improved strategy achieves a 75-fold reduction in the computational cost for a 20 zone model. The faster strategies achieve their cost savings with no significant loss of accuracy. The pressure, temperature and major species mass fractions agree with the solution from the original integration approach to within six significant digits; and the radical mass fractions agree with the original solution to within four significant digits. The faster strategies effectively change the cost scaling of the multizone model from cubic to quadratic, with respect to the number of zones. As a consequence of the improved scaling, the 40 zone model offers more than a 250-fold cost savings over the basic calculation.

  7. Approximate method for stochastic chemical kinetics with two-time scales by chemical Langevin equations.

    Science.gov (United States)

    Wu, Fuke; Tian, Tianhai; Rawlings, James B; Yin, George

    2016-05-01

    The frequently used reduction technique is based on the chemical master equation for stochastic chemical kinetics with two-time scales, which yields the modified stochastic simulation algorithm (SSA). For the chemical reaction processes involving a large number of molecular species and reactions, the collection of slow reactions may still include a large number of molecular species and reactions. Consequently, the SSA is still computationally expensive. Because the chemical Langevin equations (CLEs) can effectively work for a large number of molecular species and reactions, this paper develops a reduction method based on the CLE by the stochastic averaging principle developed in the work of Khasminskii and Yin [SIAM J. Appl. Math. 56, 1766-1793 (1996); ibid. 56, 1794-1819 (1996)] to average out the fast-reacting variables. This reduction method leads to a limit averaging system, which is an approximation of the slow reactions. Because in the stochastic chemical kinetics, the CLE is seen as the approximation of the SSA, the limit averaging system can be treated as the approximation of the slow reactions. As an application, we examine the reduction of computation complexity for the gene regulatory networks with two-time scales driven by intrinsic noise. For linear and nonlinear protein production functions, the simulations show that the sample average (expectation) of the limit averaging system is close to that of the slow-reaction process based on the SSA. It demonstrates that the limit averaging system is an efficient approximation of the slow-reaction process in the sense of the weak convergence. PMID:27155630

  8. Kinetic parameters and TL mechanism in cadmium tetra borate phosphor

    Energy Technology Data Exchange (ETDEWEB)

    Annalakshmi, O. [Radiological Safety Division, Materials Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam-603102 (India); Jose, M.T., E-mail: mtj@igcar.gov.in [Radiological Safety Division, Materials Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam-603102 (India); Sridevi, J. [Central Leather Research Institute, Council of Scientific and Industrial Research, Chennai 600 020, Tamilnadhu (India); Venkatraman, B. [Radiological Safety Division, Materials Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam-603102 (India); Amarendra, G. [Materials Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam-603102 (India); Mandal, A.B. [Central Leather Research Institute, Council of Scientific and Industrial Research, Chennai 600 020, Tamilnadhu (India)

    2014-03-15

    Polycrystalline powder samples of cadmium tetra borate were synthesized by a simple solid state sintering technique and gamma irradiated sample showed a simple Thermoluminescence (TL) glow peak around 460 K. The TL kinetic parameters of gamma irradiated phosphor were determined by initial rise (IR), isothermal decay (ID), peak shape (PS), variable heating rate (VHR) and glow curve de-convolution method. The kinetic parameters such as activation energy (E), frequency factor (s) and order of kinetics (b) were calculated by IR, ID, PS and VHR methods are in the order of ∼1.05 eV, 10{sup 9}–10{sup 12} s{sup −1} and 1.58, respectively. From the results of TL and PL emission studies carried out on the phosphor revealed that the defect centers related to TL is different from that for PL. EPR measurements were carried out to identify the defect centers formed in cadmium tetra borate phosphor on gamma irradiation. Based on EPR studies the mechanism for TL process in cadmium tetra borate is proposed in this paper -- Highlights: • Polycrystalline powder samples of undoped cadmium tetra borate synthesized. • Cadmium tetra borate phosphor exhibits a dosimetric peak at 458 K. • Kinetic parameters of the trap responsible for TL evaluated. • TL mechanism is proposed from TL to EPR correlation studies.

  9. Critical evaluation of Jet-A spray combustion using propane chemical kinetics in gas turbine combustion simulated by KIVA-2

    Science.gov (United States)

    Nguyen, H. L.; Ying, S.-J.

    1990-07-01

    Jet-A spray combustion has been evaluated in gas turbine combustion with the use of propane chemical kinetics as the first approximation for the chemical reactions. Here, the numerical solutions are obtained by using the KIVA-2 computer code. The KIVA-2 code is the most developed of the available multidimensional combustion computer programs for application of the in-cylinder combustion dynamics of internal combustion engines. The released version of KIVA-2 assumes that 12 chemical species are present; the code uses an Arrhenius kinetic-controlled combustion model governed by a four-step global chemical reaction and six equilibrium reactions. Researchers efforts involve the addition of Jet-A thermophysical properties and the implementation of detailed reaction mechanisms for propane oxidation. Three different detailed reaction mechanism models are considered. The first model consists of 131 reactions and 45 species. This is considered as the full mechanism which is developed through the study of chemical kinetics of propane combustion in an enclosed chamber. The full mechanism is evaluated by comparing calculated ignition delay times with available shock tube data. However, these detailed reactions occupy too much computer memory and CPU time for the computation. Therefore, it only serves as a benchmark case by which to evaluate other simplified models. Two possible simplified models were tested in the existing computer code KIVA-2 for the same conditions as used with the full mechanism. One model is obtained through a sensitivity analysis using LSENS, the general kinetics and sensitivity analysis program code of D. A. Bittker and K. Radhakrishnan. This model consists of 45 chemical reactions and 27 species. The other model is based on the work published by C. K. Westbrook and F. L. Dryer.

  10. Degradation kinetics and mechanisms of phenolin photo-Fenton process

    Institute of Scientific and Technical Information of China (English)

    何锋; 雷乐成

    2004-01-01

    Phenol degradation in photochemically enhanced Fenton process was investigated in this work. UV-VIS spectra of phenol degradation showed the difference between photo-Fenton process and UV/H2O2, which is a typical hydroxyl radical process. A possible pathway diagram for phenol degradation in photo-Fenton process was proposed, and a mathematical model for chemical oxygen demand (COD) removal was developed. Operating parameters such as dosage of H2O2 and ferrous ions, pH, suitable carrier gas were found to impact the removal of COD significantly. The results and analysis of kinetic parameters calculated from the kinetic model showed that complex degradation of phenol was the main pathway for removal of COD: while hydroxyl radicals acted weakly in the photo-Fenton degradation of phenol.

  11. Stochastic chemical kinetics theory and (mostly) systems biological applications

    CERN Document Server

    Érdi, Péter

    2014-01-01

    This volume reviews the theory and simulation methods of stochastic kinetics by integrating historical and recent perspectives, presents applications, mostly in the context of systems biology and also in combustion theory. In recent years, due to the development in experimental techniques, such as optical imaging, single cell analysis, and fluorescence spectroscopy, biochemical kinetic data inside single living cells have increasingly been available. The emergence of systems biology brought renaissance in the application of stochastic kinetic methods.

  12. GENERAL EQUATIONS OF CARBONIZATION OF EUCALYPTUS SPP KINETIC MECHANISMS

    OpenAIRE

    Túlio Jardim Raad; Paulo César da C. Pinheiro; Maria Irene Yoshida

    2006-01-01

    In the present work, a set of general equations related to kinetic mechanism of wood compound carbonization: hemicelluloses, cellulose and lignin was obtained by Avrami-Eroffev and Arrhenius equations and Thermogravimetry of Eucalyptus cloeziana, Eucalyptus camaldulensis, Corymbia citriodora, Eucalyptus urophylla and Eucalyptus grandis samples, TG-Isothermal and TG-Dynamic. The different thermal stabilities and decomposition temperature bands of those species compounds were applied as strateg...

  13. Significance of Xenobiotic Metabolism for Bioaccumulation Kinetics of Organic Chemicals in Gammarus pulex

    OpenAIRE

    Ashauer, Roman; Hintermeister, Anita; O’Connor, Isabel; Elumelu, Maline; Hollender, Juliane; Escher, Beate I

    2012-01-01

    Bioaccumulation and biotransformation are key toxicokinetic processes that modify toxicity of chemicals and sensitivity of organisms. Bioaccumulation kinetics vary greatly among organisms and chemicals; thus, we investigated the influence of biotransformation kinetics on bioaccumulation in a model aquatic invertebrate using fifteen 14C-labeled organic xenobiotics from diverse chemical classes and physicochemical properties (1,2,3-trichlorobenzene, imidacloprid, 4,6-dinitro-o-cresol, ethylacry...

  14. A detailed chemical kinetic model for pyrolysis of the lignin model compound chroman

    Directory of Open Access Journals (Sweden)

    James Bland

    2013-12-01

    Full Text Available The pyrolysis of woody biomass, including the lignin component, is emerging as a potential technology for the production of renewable fuels and commodity chemicals. Here we describe the construction and implementation of an elementary chemical kinetic model for pyrolysis of the lignin model compound chroman and its reaction intermediate ortho-quinone methide (o-QM. The model is developed using both experimental and theoretical data, and represents a hybrid approach to kinetic modeling that has the potential to provide molecular level insight into reaction pathways and intermediates while accurately describing reaction rates and product formation. The kinetic model developed here can replicate all known aspects of chroman pyrolysis, and provides new information on elementary reaction steps. Chroman pyrolysis is found to proceed via an initial retro-Diels–Alder reaction to form o-QM + ethene (C2H4, followed by dissociation of o-QM to the C6H6 isomers benzene and fulvene (+ CO. At temperatures of around 1000–1200 K and above fulvene rapidly isomerizes to benzene, where an activation energy of around 270 kJ mol-1 is required to reproduce experimental observations. A new G3SX level energy surface for the isomerization of fulvene to benzene supports this result. Our modeling also suggests that thermal decomposition of fulvene may be important at around 950 K and above. This study demonstrates that theoretical protocols can provide a significant contribution to the development of kinetic models for biomass pyrolysis by elucidating reaction mechanisms, intermediates, and products, and also by supplying realistic rate coefficients and thermochemical properties.

  15. Effect of Chemicals on Chemical Mechanical Polishing of Glass Substrates

    Institute of Scientific and Technical Information of China (English)

    WANG Liang-Yong; ZHANG Kai-Liang; SONG Zhi-Tang; FENG Song-Lin

    2007-01-01

    @@ We investigate the effect of chemicals on chemical mechanical polishing (CMP) of glass substrates. Ceria slurry in an ultra-low concentration of 0.25wt.% is used and characterized by scanning electron microscopy. Three typical molecules, i.e. acetic acid, citric acid and sodium acrylic polymer, are adopted to investigate the effect on CMP performance in terms of material removal rate (MRR) and surface quality. The addition of sodium acrylic polymer shows the highest MRR as well as the best surface by atomic force microscopy after CMP, vhile the addition of citric acid shows the worst performance. These results reveal a mechanism that a long-chain molecule without any branches rather than small molecules and common molecules with ramose abundant-electron groups is better for the dispersion of the slurry and thus better for the CMP process.

  16. High-Pressure Turbulent Flame Speeds and Chemical Kinetics of Syngas Blends with and without Impurities

    Energy Technology Data Exchange (ETDEWEB)

    Peterson, Eric; Mathieu, Olivier; Morones, Anibal; Ravi, Sankar; Keesee, Charles; Hargis, Joshua; Vivanco, Jose

    2014-12-01

    This Topical Report documents the first year of the project, from October 1, 2013 through September 30, 2014. Efforts for this project included experiments to characterize the atmospheric-pressure turbulent flame speed vessel over a range of operating conditions (fan speeds and turbulent length scales). To this end, a new LDV system was acquired and set up for the detailed characterization of the turbulence field. Much progress was made in the area of impurity kinetics, which included a numerical study of the effect of impurities such as NO2, NO, H2S, and NH3 on ignition delay times and laminar flame speeds of syngas blends at engine conditions. Experiments included a series of laminar flame speed measurements for syngas (CO/H2) blends with various levels of CH4 and C2H6 addition, and the results were compared to the chemical kinetics model of NUI Galway. Also, a final NOx kinetics mechanism including ammonia was assembled, and a journal paper was written and is now in press. Overall, three journal papers and six conference papers related to this project were published this year. Finally, much progress was made on the design of the new high-pressure turbulent flame speed facility. An overall design that includes a venting system was decided upon, and the detailed design is in progress.

  17. Reaction route graphs. III. Non-minimal kinetic mechanisms.

    Science.gov (United States)

    Fishtik, Ilie; Callaghan, Caitlin A; Datta, Ravindra

    2005-02-24

    The concept of reaction route (RR) graphs introduced recently by us for kinetic mechanisms that produce minimal graphs is extended to the problem of non-minimal kinetic mechanisms for the case of a single overall reaction (OR). A RR graph is said to be minimal if all of the stoichiometric numbers in all direct RRs of the mechanism are equal to +/-1 and non-minimal if at least one stoichiometric number in a direct RR is non-unity, e.g., equal to +/-2. For a given mechanism, four unique topological characteristics of RR graphs are defined and enumerated, namely, direct full routes (FRs), empty routes (ERs), intermediate nodes (INs), and terminal nodes (TNs). These are further utilized to construct the RR graphs. One algorithm involves viewing each IN as a central node in a RR sub-graph. As a result, the construction and enumeration of RR graphs are reduced to the problem of balancing the peripheral nodes in the RR sub-graphs according to the list of FRs, ERs, INs, and TNs. An alternate method involves using an independent set of RRs to draw the RR graph while satisfying the INs and TNs. Three examples are presented to illustrate the application of non-minimal RR graph theory.

  18. Mechanical and chemical properties of sewage pipes

    OpenAIRE

    Ł. Wierzbicki; M. Szymiczek

    2012-01-01

    Purpose: The purpose of this paper was to evaluate the compatibility of the physico-chemical properties of sewage pipes with the requirements of PN – EN ISO 1401-01: Plastics piping systems for non-pressure underground drainage and sewerage. This article is based on a research carried out for the water supply company. The article presents the results of mechanical and chemical testing of four pipes of unplasticized polyvinyl chloride and one pipe of polypropylene. All the test pipes were app...

  19. Kinetics and mechanism of the oxidation of amaranth with hypochlorite.

    Science.gov (United States)

    Nadupalli, S; Koorbanally, N; Jonnalagadda, S B

    2011-07-14

    The reaction mechanism of the oxidation of Amaranth dye (2-hydroxy-1-(4-sulfonato-1-naphthylazo) naphthalene-3,6-disulfonate) with hypochlorite under varied pH conditions was elucidated by a kinetic approach. Under excess concentration of oxidant, the reaction followed pseudo-first-order kinetics with respect to Amaranth, and the oxidation was found to occur through two competitive reactions, initiated by hypochlorite and hypochlorous acid. The reaction order with respect to both OCl(-) ion and HOCl was unity. While the latter reaction was fast, the significance of the oxidation paths depended on the relative concentration of the two oxidizing species, which was dictated by the reaction pH. The role of the H(+) ion in the reaction was established. For the hypochlorite ion and hypochlorous acid facilitated reactions, the second-order rate coefficients were 1.9 and 23.2 M(-1) s(-1), respectively. The energy parameters were E(a) = 33.7 kJ mol(-1), ΔH(‡) = 31.2 kJ mol(-1) and ΔS(‡) = -190.6 J K(-1) mol(-1) for the OCl(-) ion-driven oxidation, and E(a) = 26.9 kJ mol(-1), ΔH(‡) = 24.3 kJ mol(-1) and ΔS(‡) = -222.8 J K(-1) mol(-1) for the reaction with HOCl-initiated oxidation. The major oxidation products for both the pathways were 3,4-dihydroxy naphthalene-2,7-disulfonic sodium salt (P(1)), dichloro-1,4-naphthoquione (P(2)) and naphtha(2,3)oxirene-2, 3-dione (P(3)). On the basis of the primary salt effect and other kinetic data, the rate law for the overall reaction and probable reaction mechanism was elucidated. The proposed mechanism was validated by simulations using Simkine-2.

  20. New Chemical Kinetics Approach for DSMC Applications to Nonequilibrium Flows Project

    Data.gov (United States)

    National Aeronautics and Space Administration — A new chemical kinetics model and database will be developed for aerothermodynamic analyses on entry vehicles. Unique features of this model include (1) the ability...

  1. Program Helps To Determine Chemical-Reaction Mechanisms

    Science.gov (United States)

    Bittker, D. A.; Radhakrishnan, K.

    1995-01-01

    General Chemical Kinetics and Sensitivity Analysis (LSENS) computer code developed for use in solving complex, homogeneous, gas-phase, chemical-kinetics problems. Provides for efficient and accurate chemical-kinetics computations and provides for sensitivity analysis for variety of problems, including problems involving honisothermal conditions. Incorporates mathematical models for static system, steady one-dimensional inviscid flow, reaction behind incident shock wave (with boundary-layer correction), and perfectly stirred reactor. Computations of equilibrium properties performed for following assigned states: enthalpy and pressure, temperature and pressure, internal energy and volume, and temperature and volume. Written in FORTRAN 77 with exception of NAMELIST extensions used for input.

  2. Vulcanization Kinetics and Mechanical Properties of Ethylene Propylene Diene Monomer Thermal Insulation

    Directory of Open Access Journals (Sweden)

    Mohamad Irfan Fathurrohman

    2015-07-01

    Full Text Available The vulcanization kinetics of Ethylene-propylene diene monomer (EPDM rubber thermal insulation was studied by using rheometer under isothermal condition at different temperatures. The rheometry analysis was used to determining the cure kinetic parameters and predicting the cure time of EPDM thermal insulation. The experimental results revealed that the curing curves of EPDM thermal insulation were marching and the optimum curing time decreased with increasing the temperature. The kinetic parameters were determined from the autocatalytic model showed close fitting with the experimental results, indicating suitability of autocatalytic model in characterizing the cure kinetics. The activation energy was determined from the autocatalytic model is 46.3661 kJ mol-1. The cure time were predicted from autocatalytic model and the obtained kinetic parameter by using the relationship among degree of conversion, cure temperature, and cure time. The predictions of cure time provide information for the actual curing characteristic of EPDM thermal insulation. The mechanical properties of EPDM thermal insulation with different vulcanization temperatures showed the same hardness, tensile strength and modulus at 300%, except at temperature 70 °C, while the elongation at breaking point decreased with increasing temperature of vulcanization. © 2015 BCREC UNDIP. All rights reservedReceived: 8th April 2014; Revised: 7th January 2015; Accepted: 16th January 2015How to Cite: Fathurrohman, M.I., Maspanger, D.R., Sutrisno, S. (2015. Vulcanization Kinetics and Mechanical Properties of Ethylene Propylene Diene Monomer Thermal Insulation. Bulletin of Chemi-cal Reaction Engineering & Catalysis, 10 (2, 104-110. (doi:10.9767/bcrec.10.2.6682.104-110Permalink/DOI: http://dx.doi.org/10.9767/bcrec.10.2.6682.104-110 

  3. Mechanism and kinetics analysis of AlN combustion synthesis

    Institute of Scientific and Technical Information of China (English)

    郑永挺; 张宇民; 赫晓东; 刘长青

    2004-01-01

    Mechanism of AlN combustion synthesis was studied by DSC analysis and "quenching" experiment of combustion wave. In preheating region, Al powder melted at 660 ℃ and became spherical because of surface tension. In reaction region, Al volatilized rapidly at 1 000 ℃ and Al vapor reacted with N2 to form AlN, which nucleated and grew on the surface of AlN formed precedently as a diluent. Based on the experiment analysis,kinetics equations and modeling were established. Analysis showed the dramatic effect of temperature, aluminum particle size and nitrogen pressure on the reaction speed.

  4. Chemical bath deposition of CdS thin films: An approach to the chemical mechanism through study of the film microstructure

    Energy Technology Data Exchange (ETDEWEB)

    Dona, J.M.; Herrero, J. [CIEMAT, Madrid (Spain). Inst. de Energias Renovables

    1997-11-01

    Many papers have been published lately on chemical bath deposition of CdS (CBD-CdS) thin films and related materials due to the promising results obtained using CBD-CdS for the fabrication of thin-film solar cells. In spite of this little of the research proposes a realistic chemical mechanism for the deposition process based on the determination of kinetic parameters. In this paper the authors present an exhaustive study of the CBD-CdS kinetic from which they propose a new chemical mechanism which agrees with the kinetic parameters determined supported by heterogeneous catalysis concepts. Simultaneously, the dependence of the deposited film structure on the kinetic variables is studied and the results obtained corroborate the proposed mechanism. These studies have allowed the authors to establish a standard set of conditions for the fabrication of homogeneous and continuous very thin CdS films.

  5. Testing for supply-limited and kinetic-limited chemical erosion in field measurements of regolith production and chemical depletion

    Science.gov (United States)

    Ferrier, Ken L.; Riebe, Clifford S.; Jesse Hahm, W.

    2016-06-01

    Chemical erosion contributes solutes to oceans, influencing atmospheric CO2 and thus global climate via the greenhouse effect. Quantifying how chemical erosion rates vary with climate and tectonics is therefore vital to understanding feedbacks that have maintained Earth's environment within a habitable range over geologic time. If chemical erosion rates are strongly influenced by the availability of fresh minerals for dissolution, then there should be strong connections between climate, which is modulated by chemical erosion, and tectonic uplift, which supplies fresh minerals to Earth's surface. This condition, referred to as supply-limited chemical erosion, implies strong tectonic control of chemical erosion rates. It differs from kinetic-limited chemical erosion, in which dissolution kinetics and thus climatic factors are the dominant regulators of chemical erosion rates. Here we present a statistical method for determining whether chemical erosion of silicate-rich bedrock is supply limited or kinetic limited, as an approach for revealing the relative importance of tectonics and climate in Earth's silicate weathering thermostat. We applied this method to published data sets of mineral supply rates and regolith chemical depletion and were unable to reject the null hypothesis that chemical erosion is supply limited in 8 of 16 cases. In seven of the remaining eight cases, we found behavior that is closer to supply limited than kinetic limited, suggesting that tectonics may often dominate over climate in regulating chemical erosion rates. However, statistical power analysis shows that new measurements across a wider range of supply rates are needed to help quantify feedbacks between climate and tectonics in Earth's long-term climatic evolution.

  6. Can an electro-kinetic mechanism explain artificial earthquakes?

    Science.gov (United States)

    Cyr, Guillaume; Glover, Paul; Novikov, Victor

    2010-05-01

    Researchers of the Joint Institute for High Temperatures of the Russian Academy of Sciences have carried out a large number of current injection experiments using a 4.2 km long dipole at the Bishkek Research Station in the Chu valley area of the Kyrgyz mountains (northern Tien Shan). The current is generated using Pulsed Magneto-Hydrodynamic (MHD) generators that can produce 2800 amperes at 1350 volts for up to 12.1 seconds. They have found that the number of earthquakes in the region within 150 km of the injection site increased by over 10 standard deviations of the background seismicity. The probability of this occurring by chance is only one in every thousand million million (10^15) measurements. It is certain, therefore, that we can generate earthquakes by current injection. However, no satisfactory physical mechanism for it currently exists. Paul Glover has suggested that an electro-kinetic mechanism may be the missing causal link. In his theory the injected current creates a three-dimensional electric field in the subsurface. The electro-kinetic mechanism uses the electric field to move the pore fluid at depth. If the pore fluid flows into a fault zone it may accumulate and transiently raise the pore fluid pressure within the fault zone. It is known that increases of pore fluid pressure within fault zones more than a critical pressure of 0.05 MPa are sufficient to trigger an earthquake if the fault has sufficient accumulated strain. Earthquakes are therefore possible while the pore fluid pressure is over the critical pressure. While the electro-kinetic drive has been well studied around the world, it is uncertain if the mechanism can provide fluid pressures sufficient to trigger earthquakes up to 150 km from the injection point. In this work we present two dimensional numerical modelling of the proposed coupled mechanism using a finite element approach and using the software package Comsol Multiphysics. The initial results are promising and indicate that (i

  7. Cation Effect on Copper Chemical Mechanical Polishing

    Institute of Scientific and Technical Information of China (English)

    WANG Liang-Yong; LIU Bo; SONG Zhi-Tang; FENG Song-Lin

    2009-01-01

    We examine the effect of cations in solutions containing benzotriazole (BTA) and H2O2 on copper chemical mechanical polishing (CMP). On the base of atomic force microscopy (AFM) and material removal rate (MRR) results, it is found that ammonia shows the highest MRR as well as good surface after CMP, while KOH demon-strates the worst performance. These results reveal a mechanism that sma//molecules with lone-pairs rather than molecules with steric effect and common inorganic cations are better for copper CMP process, which is indirectly confirmed by open circuit potential (OCP).

  8. Coupling Chemical Kinetics and Flashes in Reactive, Thermal and Compositional Reservoir Simulation

    DEFF Research Database (Denmark)

    Kristensen, Morten Rode; Gerritsen, Margot G.; Thomsen, Per Grove;

    2007-01-01

    of convergence and error test failures by more than 50% compared to direct integration without the new algorithm. To facilitate the algorithmic development we construct a virtual kinetic cell model. We use implicit one-step ESDIRK (Explicit Singly Diagonal Implicit Runge-Kutta) methods for integration...... of the kinetics. The kinetic cell model serves both as a tool for the development and testing of tailored solvers as well as a testbed for studying the interactions between chemical kinetics and phase behavior. A comparison between a Kvalue correlation based approach and a more rigorous equation of state based...

  9. Uranium dioxide sintering Kinetics and mechanisms under controlled oxygen potentials

    International Nuclear Information System (INIS)

    The initial, intermediate, and final sintering stages of uranium dioxide were investigated as a function of stoichiometry and temperature by following the kinetics of the sintering reaction. Stoichiometry was controlled by means of the oxygen potential of the sintering atmosphere, which was measured continuously by solid-state oxygen sensors. Included in the kinetic study were microspheres originated from UO2 gels and UO2 pellets produced by isostatic pressing ceramic grade powders. The microspheres sintering behavior was examined using hot-stage microscopy and a specially designed high-temperature, controlled atmosphere furnace. This same furnace was employed as part of an optical dilatometer, which was utilized in the UO2 pellet sintering investigations. For controlling the deviations from stoichiometry during heat treatment, the oxygen partial pressure in the sintering atmosphere was varied by passing the gas through a Cu-Ti-Cu oxygen trap. The trap temperature determined the oxygen partial pressure of the outflowing mixture. Dry hydrogen was also used in some of the UO sub(2+x) sintering experiments. The determination of diametrial shrinkages and sintering indices was made utilizing high-speed microcinematography and ultra-microbalance techniques. It was observed that the oxygen potential has a substantial influence on the kinetics of the three sintering stages. The control of the sintering atmosphere oxygen partial pressure led to very fast densification of UO sub(2+x). Values in the interval 95.0 to 99.5% of theoretical density were reached in less than one minute. Uranium volume diffusion is the dominant mechanism in the initial and intermediate sintering stages. For the final stage, uranium grain boundary diffusion was found to be the main sintering mechanism. (Author)

  10. 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.

  11. Parallel versus off-pathway Michaelis-Menten mechanism for single-enzyme kinetics of a fluctuating enzyme

    CERN Document Server

    Kumar, Ashutosh; Dua, Arti

    2015-01-01

    Recent fluorescence spectroscopy measurements of the turnover time distribution of single-enzyme turnover kinetics of $\\beta$-galactosidase provide evidence of Michaelis-Menten kinetics at low substrate concentration. However, at high substrate concentrations, the dimensionless variance of the turnover time distribution shows systematic deviations from the Michaelis-Menten prediction. This difference is attributed to conformational fluctuations in both the enzyme and the enzyme-substrate complex and to the possibility of both parallel and off-pathway kinetics. Here, we use the chemical master equation to model the kinetics of a single fluctuating enzyme that can yield a product through either parallel or off-pathway mechanisms. An exact expression is obtained for the turnover time distribution from which the mean turnover time and randomness parameters are calculated. The parallel and off-pathway mechanisms yield strikingly different dependences of the mean turnover time and the randomness parameter on the su...

  12. 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

  13. Reactibodies generated by kinetic selection couple chemical reactivity with favorable protein dynamics.

    Science.gov (United States)

    Smirnov, Ivan; Carletti, Eugénie; Kurkova, Inna; Nachon, Florian; Nicolet, Yvain; Mitkevich, Vladimir A; Débat, Hélène; Avalle, Bérangère; Belogurov, Alexey A; Kuznetsov, Nikita; Reshetnyak, Andrey; Masson, Patrick; Tonevitsky, Alexander G; Ponomarenko, Natalia; Makarov, Alexander A; Friboulet, Alain; Tramontano, Alfonso; Gabibov, Alexander

    2011-09-20

    Igs offer a versatile template for combinatorial and rational design approaches to the de novo creation of catalytically active proteins. We have used a covalent capture selection strategy to identify biocatalysts from within a human semisynthetic antibody variable fragment library that uses a nucleophilic mechanism. Specific phosphonylation at a single tyrosine within the variable light-chain framework was confirmed in a recombinant IgG construct. High-resolution crystallographic structures of unmodified and phosphonylated Fabs display a 15-Å-deep two-chamber cavity at the interface of variable light (V(L)) and variable heavy (V(H)) fragments having a nucleophilic tyrosine at the base of the site. The depth and structure of the pocket are atypical of antibodies in general but can be compared qualitatively with the catalytic site of cholinesterases. A structurally disordered heavy chain complementary determining region 3 loop, constituting a wall of the cleft, is stabilized after covalent modification by hydrogen bonding to the phosphonate tropinol moiety. These features and presteady state kinetics analysis indicate that an induced fit mechanism operates in this reaction. Mutations of residues located in this stabilized loop do not interfere with direct contacts to the organophosphate ligand but can interrogate second shell interactions, because the H3 loop has a conformation adjusted for binding. Kinetic and thermodynamic parameters along with computational docking support the active site model, including plasticity and simple catalytic components. Although relatively uncomplicated, this catalytic machinery displays both stereo- and chemical selectivity. The organophosphate pesticide paraoxon is hydrolyzed by covalent catalysis with rate-limiting dephosphorylation. This reactibody is, therefore, a kinetically selected protein template that has enzyme-like catalytic attributes. PMID:21896761

  14. Study on the Kinetics of Aluminum Removal from Liquid Silicon to Slag with Mechanical Stirring

    Science.gov (United States)

    Lee, Jaewoo; White, Jesse F.; Hildal, Kjetil; Sichen, Du

    2016-08-01

    The kinetics of aluminum removal from silicon melt to CaO-SiO2-Al2O3 slag was studied. A recently designed experimental setup using mechanical stirring was employed to focus the study on the chemical reaction. The slag and metal were found to reach chemical equilibrium in 300 seconds. A simple model could reproduce the experimental data satisfactorily. Both the experimental results and the model prediction further confirmed that the process was controlled by the chemical reaction, since the reaction rate constant was found to be independent of the amount of slag and the initial slag composition. The experimental data at equilibrium were compared with the model calculations. The discrepancy between the model calculations and the experimental data strongly suggests the need for careful thermodynamic measurements.

  15. Use of chemically activated cotton nut shell carbon for the removal of fluoride contaminated drinking water:Kinetics evaluation☆

    Institute of Scientific and Technical Information of China (English)

    Rajan Mariappan; Raj Vairamuthu; Alagumuthu GanapathY

    2015-01-01

    Chemically activated cotton nut shell carbons (CTNSCs) were prepared by different chemicals and they were used for the removal of fluoride from aqueous solution. Effects of adsorption time, adsorbent dose, pH of the solution, initial concentration of fluoride, and temperature of the solution were studied with equilibrium, ther-modynamics and kinetics of the adsorption process by various CTNSC adsorbents. It showed that the chemical y activated CTNSCs can effectively remove fluoride from the solution. The adsorption equilibrium data correlate well with the Freundlich isotherm model. The adsorption of fluoride by the chemical y activated CTNSC is spon-taneous and endothermic in nature. The pseudo first order, pseudo second order and intra particle diffusion kinetic models were applied to test the experimental data. The pseudo second order kinetic model provided a better correlation of the experimental data in comparison with the pseudo-first-order and intra particle diffusion models. A mechanism of fluoride adsorption associating chemisorption and physisorption processes is presented allowing the discussion of the variations in adsorption behavior between these materials in terms of specific surface area and porosity. These data suggest that chemically activated CTNSCs are promising materials for fluoride sorption.

  16. Comparison and Parametric Study of Flameless Oxidation in a Gas Turbine Using Two Kinetics Mechanisms

    Directory of Open Access Journals (Sweden)

    Mohamed Hamdi

    2008-01-01

    Full Text Available The so-called “Flameless Oxidation” is a novel combustion mode, in which combustion products are re-circulated and mixed into the fresh incoming fuel and air streams. This reduces the concentration of the reactants and thereby reducing the reaction rate through avoiding the formation of sharp high temperature zones in the combustion chamber. Flameless combustion has been acknowledged as one of the most interesting combustion technologies to meet both the targets of high energy efficiency and low pollutant emissions. This technology has already been successfully applied and exploited in industrial burners. The present investigation is concerned with the application of the flameless combustion mode to an adiabatic combustor, typically used in gas turbine engines. Detailed chemical kinetics calculations, by means of a specific zero-dimensional loop reactor model, have been performed to analyze its chemical aspects. The model simulates the combustor by a number of reactors that represent different zones in the combustion chamber. The main objective of this study is to increase the understanding of NOx formation from flameless mode, where currently very few experimental data are available. The investigation is focused on a comparison of the influence of pressure, residence time and temperature on the NOx and CO emissions, using two reaction mechanisms of the C/H/O/N system: the Miller-Bowman mechanism and the GRI_MECH3.0 mechanism. Simulation results clearly illustrate that even at high operating temperatures and pressures, NOx emissions could be reduced by flameless combustion to very low levels. A comparison between the predictions obtained by using the two chemical kinetics mechanisms is presented and discussed. It is shown that the predictions of the Miller-Bowman mechanism deviate from the predictions of the GRI3.0 mechanism in many aspects, especially as related to NOx emission results.

  17. Chemical Kinetic Study of Nitrogen Oxides Formation Trends in Biodiesel Combustion

    Directory of Open Access Journals (Sweden)

    Junfeng Yang

    2012-01-01

    Full Text Available The use of biodiesel in conventional diesel engines results in increased NOx emissions; this presents a barrier to the widespread use of biodiesel. The origins of this phenomenon were investigated using the chemical kinetics simulation tool: CHEMKIN-2 and the CFD KIVA3V code, which was modified to account for the physical properties of biodiesel and to incorporate semidetailed mechanisms for its combustion and the formation of emissions. Parametric ϕ-T maps and 3D engine simulations were used to assess the impact of using oxygen-containing fuels on the rate of NO formation. It was found that using oxygen-containing fuels allows more O2 molecules to present in the engine cylinder during the combustion of biodiesel, and this may be the cause of the observed increase in NO emissions.

  18. Optimization of a Reduced Chemical Kinetic Model for HCCI Engine Simulations by Micro-Genetic Algorithm

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    A reduced chemical kinetic model (44 species and 72 reactions) for the homogeneous charge compression ignition (HCCI) combustion of n-heptane was optimized to improve its autoignition predictions under different engine operating conditions. The seven kinetic parameters of the optimized model were determined by using the combination of a micro-genetic algorithm optimization methodology and the SENKIN program of CHEMKIN chemical kinetics software package. The optimization was performed within the range of equivalence ratios 0.2-1.2, initial temperature 310-375 K and initial pressure 0.1-0.3 MPa. The engine simulations show that the optimized model agrees better with the detailed chemical kinetic model (544 species and 2 446 reactions) than the original model does.

  19. Chemical Dynamics, Molecular Energetics, and Kinetics at the Synchrotron

    OpenAIRE

    Leone, Stephen R.

    2010-01-01

    Scientists at the Chemical Dynamics Beamline of the Advanced Light Source in Berkeley are continuously reinventing synchrotron investigations of physical chemistry and chemical physics with vacuum ultraviolet light. One of the unique aspects of a synchrotron for chemical physics research is the widely tunable vacuum ultraviolet light that permits threshold ionization of large molecules with minimal fragmentation. This provides novel opportunities to assess molecular energetics and reaction me...

  20. Solving stochastic chemical kinetics by Metropolis Hastings sampling

    OpenAIRE

    Moosavi, Azam S. Zavar; Tranquilli, Paul; Sandu, Adrian

    2014-01-01

    This study considers using Metropolis-Hastings algorithm for stochastic simulation of chemical reactions. The proposed method uses SSA (Stochastic Simulation Algorithm) distribution which is a standard method for solving well-stirred chemically reacting systems as a desired distribution. A new numerical solvers based on exponential form of exact and approximate solutions of CME (Chemical Master Equation) is employed for obtaining target and proposal distributions in Metropolis-Hastings algori...

  1. Mechanisms of fuel-cladding chemical interaction: US interpretation

    International Nuclear Information System (INIS)

    Proposed mechanisms of fuel-cladding chemical interaction (FCCI) in LMFBR fuel pins are reviewed and examined in terms of in-pile and out-of-pile data. From this examination several factors are identified which may govern the occurrence of localized deep intergranular penetrations of Type-316SS cladding. Using a plausible mechanistic hypothesis for FCCI, first steps have been taken towards developing a quantitative, physically-meaningful, mathematical method of predicting cladding wastage in operating fuel pins. Both kinetic and thermodynamic aspects of FCCI are considered in the development of this prediction method, together with a fuel chemistry model that describes the evolution of thermochemical conditions at the fuel-cladding gap. On the basis of results from recent fuel pin and laboratory tests a thermal transport mechanism has been proposed to explain the thermal gradient-induced migration of Fe, Cr, and Ni from cladding into the fuel. This mechanism involves chemical transport of the metallic cladding components (as tellurides) in liquid Cs-Te. (author)

  2. Chemical kinetic study of the oxidation of a biodiesel-bioethanol surrogate fuel: methyl octanoate-ethanol mixtures.

    Science.gov (United States)

    Togbé, C; May-Carle, J-B; Dayma, G; Dagaut, P

    2010-03-25

    There is a growing interest for using bioethanol-biodiesel fuel blends in diesel engines but no kinetic data and model for their combustion were available. Therefore, the kinetics of oxidation of a biodiesel-bioethanol surrogate fuel (methyl octanoate-ethanol) was studied experimentally in a jet-stirred reactor at 10 atm and constant residence time, over the temperature range 560-1160 K, and for several equivalence ratios (0.5-2). Concentration profiles of reactants, stable intermediates, and final products were obtained by probe sampling followed by online FTIR, and off-line gas chromatography analyses. The oxidation of this fuel in these conditions was modeled using a detailed chemical kinetic reaction mechanism consisting of 4592 reversible reactions and 1087 species. The proposed kinetic reaction mechanism yielded a good representation of the kinetics of oxidation of this biodiesel-bioethanol surrogate under the JSR conditions. The modeling was used to delineate the reactions triggering the low-temperature oxidation of ethanol important for diesel engine applications. PMID:20235606

  3. Chemical Mechanical Polishing of Silicon Carbide

    Science.gov (United States)

    Powell, J. Anthony; Pirouz

    1999-01-01

    The High Temperature Integrated Electronics and Sensors (HTIES) team at the NASA Lewis Research Center is developing silicon carbide (SiC) as an enabling electronic technology for many aerospace applications. The Lewis team is focusing on the chemical vapor deposition of the thin, single-crystal SiC films from which devices are fabricated. These films, which are deposited (i.e., epitaxially "grown") on commercial wafers, must consist of a single crystal with very few structural defects so that the derived devices perform satisfactorily and reliably. Working in collaboration (NASA grant) with Professor Pirouz of Case Western Reserve University, we developed a chemical-mechanical polishing (CMP) technique for removing the subsurface polishing damage prior to epitaxial growth of the single-crystal SiC films.

  4. Hydrodenitrogenation mechanism of aromatic amines. Kinetic study and simulation

    International Nuclear Information System (INIS)

    The decomposition of model molecules reacting alone or in competition was studied in a fixed bed reactor at 623 K and 7 MPa over a sulfided NiMo/Al2O3 catalyst. The inhibiting effect of H2S and some nitrogen molecules, namely quinoline type compounds plays a major role in the transformation of anilines intermediates. On the other hand H2S acts as a cocatalyst and promote carbon-nitrogen bond cleavage, specially at low H2S partial pressure. When the H2S partial pressure is greater than the nitrogen compound partial pressure an inhibiting effect of H2S occurs and its promoting effect on carbon-nitrogen bond cleavage is cancelled. Hydrogen has a positive but moderate effect in hydrogenation steps. The mechanism of carbon-nitrogen bond scission depends on the structure of the nitrogen molecule namely on the hybridization of the carbon atom bearing the nitrogen atom. If the carbon a with respect to the nitrogen is monosubstituted the mechanism is essentially a nucleophilic substitution. When the degree of substitution increases the elimination mechanism becomes more important and the two mechanisms are in competition. With a sulfided catalyst, H2S from the gas phase doesn't change the importance of each mechanism, it just increases the rate of the reaction. In the presence of an oxide catalyst the contribution of the two mechanisms change. This result shows the importance of the sulphur species from the surface. Using isotopic exchange we could demonstrate that the sites able to dissociate H2S and H2 are the same, and that the dissociation is of heterolytic nature. The kinetic modeling of hydrotreatment reactions using the CHEMKIN/SURFACE CHEMKIN package seems to be a convenient method in order to understand the kinetic and mechanistic phenomena in hydrodenitrogenation. The preliminary simulations in the case of 2.6 diethylaniline showed that only one type of site is not sufficient in order to account for the experimental results. Further simulations will be necessary

  5. Kinetics and mechanism of methane oxidation in supercritical water

    International Nuclear Information System (INIS)

    This project, is a Hazardous Waste Remedial Actions Program (HAZWRAP) Research and Development task being carried out by the Los Alamos National Laboratory. Its objective is to achieve an understanding of the technology for use in scaling up and applying oxidation in supercritical water as a viable process for treating a variety of Department of Energy Defense Programs (DOE-DP) waste streams. This report presents experimental results for the kinetics of the oxidation of methane and methanol in supercritical water and computer modeling results for the oxidation of carbonmonoxide and methane in supercritical water. The experimental and modeling results obtained to date on these one-carbon model compounds indicate that the mechanism of oxidation in supercritical water can be represented by free-radical reactions with appropriate modifications for high pressure and the high water concentration. If these current trends are sustained, a large body of existing literature data on the kinetics of elementary reactions can be utilized to predict the behavior of other compounds and their mixtures. 7 refs., 4 figs., 3 tabs

  6. CFD analysis of municipal solid waste combustion using detailed chemical kinetic modelling.

    Science.gov (United States)

    Frank, Alex; Castaldi, Marco J

    2014-08-01

    Nitrogen oxides (NO x ) emissions from the combustion of municipal solid waste (MSW) in waste-to-energy (WtE) facilities are receiving renewed attention to reduce their output further. While NO x emissions are currently 60% below allowed limits, further reductions will decrease the air pollution control (APC) system burden and reduce consumption of NH3. This work combines the incorporation of the GRI 3.0 mechanism as a detailed chemical kinetic model (DCKM) into a custom three-dimensional (3D) computational fluid dynamics (CFD) model fully to understand the NO x chemistry in the above-bed burnout zones. Specifically, thermal, prompt and fuel NO formation mechanisms were evaluated for the system and a parametric study was utilized to determine the effect of varying fuel nitrogen conversion intermediates between HCN, NH3 and NO directly. Simulation results indicate that the fuel nitrogen mechanism accounts for 92% of the total NO produced in the system with thermal and prompt mechanisms accounting for the remaining 8%. Results also show a 5% variation in final NO concentration between HCN and NH3 inlet conditions, demonstrating that the fuel nitrogen intermediate assumed is not significant. Furthermore, the conversion ratio of fuel nitrogen to NO was 0.33, revealing that the majority of fuel nitrogen forms N2. PMID:25005043

  7. The promising chemical kinetics for the simulation of propane-air combustion with KIVA-II code

    Science.gov (United States)

    Ying, S. J.; Gorla, Rama S. R.; Kundu, Krishna P.

    1993-01-01

    The development of chemical kinetics for the simulation of propane-air combustion with the use of computer code KIVA-II since 1989 is summarized here. In order to let readers understand the general feature well, a brief description of the KIVA-II code, specially related with the chemical reactions is also given. Then the results of recent work with 20 reaction mechanism is presented. It is also compared with the 5 reaction mechanism. It may be expected that the numerical stability of the 20 reaction mechanism is better as compared to that of 5 reaction mechanism, but the CPU time of the CRAY computer is much longer. Details are presented in the paper.

  8. Tribology analysis of chemical-mechanical polishing

    Energy Technology Data Exchange (ETDEWEB)

    Runnels, S.R.; Eyman, L.M. (Sematech, Austin, TX (United States))

    1994-06-01

    To better understand the variation of material removal rate on a wafer during chemical-mechanical polishing (CMP), knowledge of the stress distribution on the wafer surface is required. The difference in wafer-surface stress distributions could be considerable depending on whether or not the wafer hydroplanes during polishing. This study analyzes the fluid film between the wafer and pad and demonstrates that hydroplaning is possible for standard CMP processes. The importance of wafer curvature, slurry viscosity, and rotation speed on the thickness of the fluid film is also demonstrated.

  9. Mechanical and Chemical Signaling in Angiogenesis

    CERN Document Server

    2013-01-01

    This volume of Studies in Mechanobiology, Tissue Engineering and Biomaterials describes the most recent advances in angiogenesis research at all biological length scales: molecular, cellular and tissue, in both in vivo and in vitro settings.  Angiogenesis experts from diverse fields including engineering, cell and developmental biology, and chemistry have contributed chapters which focus on the mechanical and chemical signals which affect and promote blood vessel growth. Specific emphasis is given to novel methodologies and biomaterials that have been developed and applied to angiogenesis research. 

  10. Reaction diffusion and solid state chemical kinetics handbook

    CERN Document Server

    Dybkov, V I

    2010-01-01

    This monograph deals with a physico-chemical approach to the problem of the solid-state growth of chemical compound layers and reaction-diffusion in binary heterogeneous systems formed by two solids; as well as a solid with a liquid or a gas. It is explained why the number of compound layers growing at the interface between the original phases is usually much lower than the number of chemical compounds in the phase diagram of a given binary system. For example, of the eight intermetallic compounds which exist in the aluminium-zirconium binary system, only ZrAl3 was found to grow as a separate

  11. 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.

  12. Kinetics mechanism of microwave sintering in ceramic materials

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Based on the traditional sintering model incorporating the characteristic of microwave sintering, the ionic conductance diffusion mechanism in microwave sintering was studied. A flat-ball model was presented to describe the kinetics process in microwave sintering, and was applied to the sintering process of TZP and ZrO2-Al2O3 ceramics. The results indicate that the shrinkage rate of materials in microwave sintering is proportional to t2/3 and r-4/3, respectively, where t is the sintering time and r is the particle radius. Whereas, the shrinkage rate of materials in conventional sintering is proportional to sintering time t2/5. Our model suggests that microwave sintering is faster than conventional sintering, which shows a good agreement with the experimental observation in sintering process of TZP and ZrO2-Al2O3.

  13. Validity conditions for moment closure approximations in stochastic chemical kinetics

    OpenAIRE

    Schnoerr, David; Sanguinetti, Guido; Grima, Ramon

    2014-01-01

    Approximations based on moment-closure (MA) are commonly used to obtain estimates of the mean molecule numbers and of the variance of fluctuations in the number of molecules of chemical systems. The advantage of this approach is that it can be far less computationally expensive than exact stochastic simulations of the chemical master equation. Here, we numerically study the conditions under which the MA equations yield results reflecting the true stochastic dynamics of the system. We show tha...

  14. Validity conditions for moment closure approximations in stochastic chemical kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Schnoerr, David [School of Biological Sciences, University of Edinburgh, Edinburgh EH9 3JR (United Kingdom); School of Informatics, University of Edinburgh, Edinburgh EH8 9LE (United Kingdom); Sanguinetti, Guido [School of Informatics, University of Edinburgh, Edinburgh EH8 9LE (United Kingdom); Grima, Ramon [School of Biological Sciences, University of Edinburgh, Edinburgh EH9 3JR (United Kingdom)

    2014-08-28

    Approximations based on moment-closure (MA) are commonly used to obtain estimates of the mean molecule numbers and of the variance of fluctuations in the number of molecules of chemical systems. The advantage of this approach is that it can be far less computationally expensive than exact stochastic simulations of the chemical master equation. Here, we numerically study the conditions under which the MA equations yield results reflecting the true stochastic dynamics of the system. We show that for bistable and oscillatory chemical systems with deterministic initial conditions, the solution of the MA equations can be interpreted as a valid approximation to the true moments of the chemical master equation, only when the steady-state mean molecule numbers obtained from the chemical master equation fall within a certain finite range. The same validity criterion for monostable systems implies that the steady-state mean molecule numbers obtained from the chemical master equation must be above a certain threshold. For mean molecule numbers outside of this range of validity, the MA equations lead to either qualitatively wrong oscillatory dynamics or to unphysical predictions such as negative variances in the molecule numbers or multiple steady-state moments of the stationary distribution as the initial conditions are varied. Our results clarify the range of validity of the MA approach and show that pitfalls in the interpretation of the results can only be overcome through the systematic comparison of the solutions of the MA equations of a certain order with those of higher orders.

  15. Chemically Locked Bicelles with High Thermal and Kinetic Stability.

    Science.gov (United States)

    Matsui, Ryoichi; Ohtani, Masataka; Yamada, Kuniyo; Hikima, Takaaki; Takata, Masaki; Nakamura, Takashi; Koshino, Hiroyuki; Ishida, Yasuhiro; Aida, Takuzo

    2015-11-01

    In situ polymerization of a bicellar mixture composed of a phospholipid and polymerizable surfactants afforded unprecedented stable bicelles. The polymerized composite showed an aligned phase over a wide thermal range (25 to >90 °C) with excellent (2)H quadrupole splitting of the solvent signal, thus implying versatility as an alignment medium for NMR studies. Crosslinking of the surfactants also brought favorable effects on the kinetic stability and alignment morphology of the bicelles. This system could thus offer a new class of scaffolds for biomembrane models. PMID:26373898

  16. KINETICS OF CHEMICAL TRANSFORMATIONS OF HYDROCARBONS WORKING LIQUID FH-51 AT OPERATING AIRCRAFT

    OpenAIRE

    Кузнєцова, О.; Національний авіаційний університет; Нетреба, Ж.; Національний авіаційний університет

    2013-01-01

    Today the French hydraulic liquid «Hydronicoil» FH-51 is used in aircraft hydrosystems of Ukraine airlines.During aircraft exploitation under the action of external factors there are chemical transformations in molecules of liquid hydrocarbons. Research on kinetics of chemical transformations of hydrocarbons of working liquidFH-51 is carried out. The model of the noted chemical transformations, which provide achievement of necessary quality level of the liquid and aircraft reliability, is fou...

  17. VULCAN: an Open-Source, Validated Chemical Kinetics Python Code for Exoplanetary Atmospheres

    OpenAIRE

    Tsai, Shang-Min; Lyons, James R.; Grosheintz, Luc; Rimmer, Paul B.; Kitzmann, Daniel; Heng, Kevin

    2016-01-01

    We present an open-source and validated chemical kinetics code for studying hot exoplanetary atmospheres, which we name VULCAN. It is constructed for gaseous chemistry from 500 to 2500 K using a reduced C- H-O chemical network with about 300 reactions. It uses eddy diffusion to mimic atmospheric dynamics and excludes photochemistry. We have provided a full description of the rate coefficients and thermodynamic data used. We validate VULCAN by reproducing chemical equilibrium and by comparing ...

  18. A Gas-Kinetic Scheme for Multimaterial Flows and Its Application in Chemical Reaction

    Science.gov (United States)

    Lian, Yongsheng; Xu, Kun

    1999-01-01

    This paper concerns the extension of the multicomponent gas-kinetic BGK-type scheme to multidimensional chemical reactive flow calculations. In the kinetic model, each component satisfies its individual gas-kinetic BGK equation and the equilibrium states of both components are coupled in space and time due to the momentum and energy exchange in the course of particle collisions. At the same time, according to the chemical reaction rule one component can be changed into another component with the release of energy, where the reactant and product could have different gamma. Many numerical test cases are included in this paper, which show the robustness and accuracy of kinetic approach in the description of multicomponent reactive flows.

  19. CERENA: ChEmical REaction Network Analyzer--A Toolbox for the Simulation and Analysis of Stochastic Chemical Kinetics.

    Science.gov (United States)

    Kazeroonian, Atefeh; Fröhlich, Fabian; Raue, Andreas; Theis, Fabian J; Hasenauer, Jan

    2016-01-01

    Gene expression, signal transduction and many other cellular processes are subject to stochastic fluctuations. The analysis of these stochastic chemical kinetics is important for understanding cell-to-cell variability and its functional implications, but it is also challenging. A multitude of exact and approximate descriptions of stochastic chemical kinetics have been developed, however, tools to automatically generate the descriptions and compare their accuracy and computational efficiency are missing. In this manuscript we introduced CERENA, a toolbox for the analysis of stochastic chemical kinetics using Approximations of the Chemical Master Equation solution statistics. CERENA implements stochastic simulation algorithms and the finite state projection for microscopic descriptions of processes, the system size expansion and moment equations for meso- and macroscopic descriptions, as well as the novel conditional moment equations for a hybrid description. This unique collection of descriptions in a single toolbox facilitates the selection of appropriate modeling approaches. Unlike other software packages, the implementation of CERENA is completely general and allows, e.g., for time-dependent propensities and non-mass action kinetics. By providing SBML import, symbolic model generation and simulation using MEX-files, CERENA is user-friendly and computationally efficient. The availability of forward and adjoint sensitivity analyses allows for further studies such as parameter estimation and uncertainty analysis. The MATLAB code implementing CERENA is freely available from http://cerenadevelopers.github.io/CERENA/.

  20. Desorption kinetics of hydrophobic organic chemicals from sediment to water: a review of data and models.

    Science.gov (United States)

    Birdwell, Justin; Cook, Robert L; Thibodeaux, Louis J

    2007-03-01

    Resuspension of contaminated sediment can lead to the release of toxic compounds to surface waters where they are more bioavailable and mobile. Because the timeframe of particle resettling during such events is shorter than that needed to reach equilibrium, a kinetic approach is required for modeling the release process. Due to the current inability of common theoretical approaches to predict site-specific release rates, empirical algorithms incorporating the phenomenological assumption of biphasic, or fast and slow, release dominate the descriptions of nonpolar organic chemical release in the literature. Two first-order rate constants and one fraction are sufficient to characterize practically all of the data sets studied. These rate constants were compared to theoretical model parameters and functionalities, including chemical properties of the contaminants and physical properties of the sorbents, to determine if the trends incorporated into the hindered diffusion model are consistent with the parameters used in curve fitting. The results did not correspond to the parameter dependence of the hindered diffusion model. No trend in desorption rate constants, for either fast or slow release, was observed to be dependent on K(OC) or aqueous solubility for six and seven orders of magnitude, respectively. The same was observed for aqueous diffusivity and sediment fraction organic carbon. The distribution of kinetic rate constant values was approximately log-normal, ranging from 0.1 to 50 d(-1) for the fast release (average approximately 5 d(-1)) and 0.0001 to 0.1 d(-1) for the slow release (average approximately 0.03 d(-1)). The implications of these findings with regard to laboratory studies, theoretical desorption process mechanisms, and water quality modeling needs are presented and discussed. PMID:17373505

  1. Chemical Reactions and Kinetics of the Carbon Monoxide Coupling in the Presence of Hydrogen

    Institute of Scientific and Technical Information of China (English)

    Fandong Meng; Genhui Xu; Zhenhua Li; Pa Du

    2002-01-01

    The chemical reactions and kinetics of the catalytic coupling reaction of carbon monoxide to diethyl oxalate were studied in the presence of hydrogen over a supported palladium catalyst in the gaseous phase at the typical coupling reaction conditions. The experiments were performed in a continuous flow fixed-bed reactor. The results indicated that hydrogen only reacts with ethyl nitrite to form ethanol, and kinetic studies revealed that the rate-determining step is the surface reaction of adsorbed hydrogen and the ethoxy radical (EtO-). A kinetic model is proposed and a comparison of the observed and calculated conversions showed that the rate expressions are of rather high confidence.

  2. RHEOLOGIC STUDIES ON CHEMICAL CROSS-LINKING KINETICS FOR LDPE

    Institute of Scientific and Technical Information of China (English)

    Hong-mei Yang; Zhi-gang Liu; Yong-zhu Yang; Qiang Zheng

    2012-01-01

    Crosslinking reaction of LDPE resin in the presence of dicumyl peroxide (DCP) was studied by isothermal rheological measurements at different temperatures and non-isothermal differential scanning calorimetry (DSC) technique with different heating rates.The kinetic parameters of crosslinking reaction were calculated by both rheological and DSC measurements.The results reveal that with the increase of DCP contents,the apparent activation energy,Ea,ranges from about 140 kJ/mol to 170 kJ/mol and the order of crosslinking reaction,(n),approaches unity.The influence of measurement frequency,ω,on crosslinking reaction was also investigated.It can be found that (n) does not change with the increase of ω,and Ea decreases slightly with the increase of ω.

  3. Determination of kinetics and stoichiometry of chemical sulfide oxidation in wastewater of sewer networks

    DEFF Research Database (Denmark)

    Nielsen, A.H.; Vollertsen, Jes; Hvitved-jacobsen, Thorkild

    2003-01-01

    A method for determination of kinetics and stoichiometry of chemical sulfide oxidation by dissolved oxygen (DO) in wastewater is presented. The method was particularly developed to investigate chemical sulfide oxidation in wastewater of sewer networks at low DO concentrations. The method is based...... parameters determined in a triplicate experiment. The kinetic parameters determined in 25 experiments on wastewater samples from a single site exhibited good constancy with a variation of the same order of magnitude as the precision of the method. It was found that the stoichiometry of the reaction could...... be considered constant during the course of the experiments although intermediates accumulated. This was explained by an apparent slow oxidation rate of the intermediates. The method was capable of determining kinetics and stoichiometry of chemical sulfide oxidation at DO concentrations lower than 1 g of O2 m...

  4. Parameter Estimates in Differential Equation Models for Chemical Kinetics

    Science.gov (United States)

    Winkel, Brian

    2011-01-01

    We discuss the need for devoting time in differential equations courses to modelling and the completion of the modelling process with efforts to estimate the parameters in the models using data. We estimate the parameters present in several differential equation models of chemical reactions of order n, where n = 0, 1, 2, and apply more general…

  5. Dicyclopalladated complexes of asymmetrically substituted azobenzenes: synthesis, kinetics and mechanisms.

    Science.gov (United States)

    Juribašić, Marina; Budimir, Ana; Kazazić, Snježana; Curić, Manda

    2013-11-01

    Two series of new dicyclopalladated complexes {(DMF)PdCl(μ-R(1)C6H3N═NC6H3R(2))PdCl(DMF)} of 4,4'-functionalized azobenzenes with substituents of varying electron-donating or electron-withdrawing strength (R(1) = H, NMe2; R(2) = H, Cl, Br, I, OMe, PhNH, CO2H, SO3Na, or NO2) have been synthesized and fully characterized. (1)H NMR spectroscopy along with the ESI mass spectrometry unambiguously identified the new complexes in the solution, and their solid-state structures were determined by X-ray crystallography. The presence of easily exchangeable solvent ligands was confirmed by (1)H NMR spectroscopy, X-ray experiments, and ESI mass spectrometry. The complexes were additionally characterized by UV-vis and fluorescence spectroscopies. The effect of different 4,4'-substituents on the formation rate of mono- and dicyclopalladated azobenzenes was studied by UV-vis spectroscopy. The experimental results are complemented by the quantum-chemical (DFT) calculations in order to rationalize the kinetic results as well as substituent effects on the reaction rates. It was found that the mono- and dicyclopalladation reactions of azobenzenes proceed in two consecutive processes, adduct formation and palladation steps. The rate-determining step in both palladations is the breaking of the ortho C-H bond, which has been confirmed as an electrophilic substitution process by Hammett correlations and DFT calculations. PMID:24116960

  6. The release behavior and kinetic evaluation of tramadol HCl from chemically cross linked Ter polymeric hydrogels

    Directory of Open Access Journals (Sweden)

    Malana Muhammad A

    2013-01-01

    Full Text Available Abstract Background and the purpose of the study Hydrogels, being stimuli responsive are considered to be effective for targeted and sustained drug delivery. The main purpose for this work was to study the release behavior and kinetic evaluation of Tramadol HCl from chemically cross linked ter polymeric hydrogels. Methods Ter-polymers of methacrylate, vinyl acetate and acrylic acid cross linked with ethylene glycol dimethacrylate (EGDMA were prepared by free radical polymerization. The drug release rates, dynamic swelling behavior and pH sensitivity of hydrogels ranging in composition from 1-10 mol% EGDMA were studied. Tramadol HCl was used as model drug substance. The release behavior was investigated at pH 8 where all formulations exhibited non-Fickian diffusion mechanism. Results and major conclusion Absorbency was found to be more than 99% indicating good drug loading capability of these hydrogels towards the selected drug substance. Formulations designed with increasing amounts of EGDMA had a decreased equilibrium media content as well as media penetrating velocity and thus exhibited a slower drug release rate. Fitting of release data to different kinetic models indicate that the kinetic order shifts from the first to zero order as the concentration of drug was increased in the medium, showing gradual independency of drug release towards its concentration. Formulations with low drug content showed best fitness with Higuchi model whereas those with higher concentration of drug followed Hixson-Crowell model with better correlation values indicating that the drug release from these formulations depends more on change in surface area and diameter of tablets than that on concentration of the drug. Release exponent (n derived from Korse-Meyer Peppas equation implied that the release of Tramadol HCl from these formulations was generally non-Fickian (n > 0.5 > 1 showing swelling controlled mechanism. The mechanical strength and controlled

  7. The Release Behavior and Kinetic Evaluation of Tramadol HCl from Chemically Cross Linked Ter Polymeric Hydrogels

    Directory of Open Access Journals (Sweden)

    Muhammad A Malana

    2013-01-01

    Full Text Available Background and the purpose of the study: Hydrogels, being stimuli responsive are considered to be effective for targeted and sustained drug delivery. The main purpose for this work was to study the release behavior and kinetic evaluation of Tramadol HCl from chemically cross linked ter polymeric hydrogels.MethodsTer-polymers of methacrylate, vinyl acetate and acrylic acid cross linked with ethylene glycol dimethacrylate (EGDMA were prepared by free radical polymerization. The drug release rates, dynamic swelling behavior and pH sensitivity of hydrogels ranging in composition from 1-10 mol % EGDMA were studied. Tramadol HCl was used as model drug substance. The release behavior was investigated at pH 8 where all formulations exhibited non-Fickian diffusion mechanism.Results and major conclusion: Absorbency was found to be more than 99% indicating good drug loading capability of these hydrogels towards the selected drug substance. Formulations designed with increasing amounts of EGDMA had a decreased equilibrium media content as well as media penetrating velocity and thus exhibited a slower drug release rate. Fitting of release data to different kinetic models indicate that the kinetic order shifts from the first to zero order as the concentration of drug was increased in the medium, showing gradual independency of drug release towards its concentration. Formulations with low drug content showed best fitness with Higuchi model whereas those with higher concentration of drug followed Hixson-Crowell model with better correlation values indicating that the drug release from these formulations depends more on change in surface area and diameter of tablets than that on concentration of the drug. Release exponent (n derived from Korse-Meyer Peppas equation implied that the release of Tramadol HCl from these formulations was generally non-Fickian (n>0.5>1 showing swelling controlled mechanism. The mechanical strength and controlled release capability of

  8. Mechanism of controlled release kinetics from medical devices

    Directory of Open Access Journals (Sweden)

    A. Raval

    2010-06-01

    Full Text Available Utilization of biodegradable polymers for controlled drug delivery has gained immense attention in the pharmaceutical and medical device industry to administer various drugs, proteins and other bio-molecules both systematically and locally to cure several diseases. The efficacy and toxicity of this local therapeutics depends upon drug release kinetics, which will further decide drug deposition, distribution, and retention at the target site. Drug Eluting Stent (DES presently possesses clinical importance as an alternative to Coronary Artery Bypass Grafting due to the ease of the procedure and comparable safety and efficacy. Many models have been developed to describe the drug delivery from polymeric carriers based on the different mechanisms which control the release phenomenon from DES. Advanced characterization techniques facilitate an understanding of the complexities behind design and related drug release behavior of drug eluting stents, which aids in the development of improved future drug eluting systems. This review discusses different drug release mechanisms, engineering principles, mathematical models and current trends that are proposed for drug-polymer coated medical devices such as cardiovascular stents and different analytical methods currently utilized to probe diverse characteristics of drug eluting devices.

  9. A steady-state kinetic analysis of the prolyl-4-hydroxylase mechanism.

    Science.gov (United States)

    Soskel, N T; Kuby, S A

    1981-01-01

    Published kinetic data by Kivirikko, et al. on the prolyl-4-hydroxylase reaction have been re-evaluated using the overall steady-state velocity equation in the forward and reverse directions for an ordered ter ter kinetic mechanism. Qualitatively, the published data for prolyl-4-hydroxylase appear to fit the predicted patterns for this kinetic mechanism. More kinetic data are needed to confirm these results and to quantitate the kinetic parameters but, tentatively, the order of substrate addition would appear to be alpha-ketoglutarate, oxygen, and peptide; and the order of product release would be hydroxylated peptide (or collagen), carbon dioxide, and succinate.

  10. EFFECTS OF SIMPLIFIED CHEMICAL KINETIC MODEL ON THE MICRO-FLAME STRUCTURE AND TEMPERATURE OF THE LEAN PREMIXED METHANE-AIR MIXTURES

    Directory of Open Access Journals (Sweden)

    JUNJIE CHEN

    2015-07-01

    Full Text Available The effect of simplified chemical kinetic model on the micro-flame structure, central axis and wall temperatures were investigated with different one-step global chemical kinetic mechanisms following Mantel, Duterque and Fernández-Tarrazo models. Numerical investigations of the premixed methane-air flame in the micro-channel and lean conditions were carried out to compare and analyze the effect of the comprehensive chemical kinetic mechanisms. The results indicate that one-step global chemical kinetic mechanism affects both the micro-flame shape and the combustion temperature. Among three simulation models, Mantel model allows a stable micro-flame with a bamboo shoot form, which anchor at the inlet. Duterque model gives a stable elongated micro-flame with a considerable ignition delay, and a dead zone with fluid accumulation is observed at the entrance, which may explain the very high combustion temperature and the fast reaction rate obtained, despite the micro-flame development presents a very hot spot and causes a broadening of the combustion zone. Fernández-Tarrazo model results in a rapid extinction and doesn't seem to take all the kinetic behavior into account for the appropriate micro-combustion simulations.

  11. Colloidal chemical synthesis and formation kinetics of uniformly sized nanocrystals of metals, oxides, and chalcogenides.

    Science.gov (United States)

    Kwon, Soon Gu; Hyeon, Taeghwan

    2008-12-01

    Nanocrystals exhibit interesting electrical, optical, magnetic, and chemical properties not achieved by their bulk counterparts. Consequently, to fully exploit the potential of nanocrystals, the synthesis of nanocrystals must focus on producing materials with uniform size and shape. Top-down physical processes can produce large quantities of nanocrystals, but controlling the size is difficult with these methods. On the other hand, colloidal chemical synthetic methods can produce uniform nanocrystals with a controlled particle size. In this Account, we present our synthesis of uniform nanocrystals of various shapes and materials, and we discuss the kinetics of nanocrystal formation. We employed four different synthetic approaches including thermal decomposition, nonhydrolytic sol-gel reactions, thermal reduction, and use of reactive chalcogen reagents. We synthesized uniform oxide nanocrystals via heat-up methods. This method involved slowly heat-up reaction mixtures composed of metal precursors, surfactants, and solvents from room temperature to high temperature. We then held reaction mixtures at an aging temperature for a few minutes to a few hours. Kinetics studies revealed a three-step mechanism for the synthesis of nanocrystals through the heat-up method with size distribution control. First, as metal precursors thermally decompose, monomers accumulate. At the aging temperature, burst nucleation occurs rapidly; at the end of this second phase, nucleation stops, but continued diffusion-controlled growth leads to size focusing to produce uniform nanocrystals. We used nonhydrolytic sol-gel reactions to synthesize various transition metal oxide nanocrystals. We employed ester elimination reactions for the synthesis of ZnO and TiO(2) nanocrystals. Uniform Pd nanoparticles were synthesized via a thermal reduction reaction induced by heating up a mixture of Pd(acac)(2), tri-n-octylphosphine, and oleylamine to the aging temperature. Similarly, we synthesized

  12. Development of multi-component diesel surrogate fuel models – Part I: Validation of reduced mechanisms of diesel fuel constituents in 0-D kinetic simulations

    DEFF Research Database (Denmark)

    Poon, Hiew Mun; Pang, Kar Mun; Ng, Hoon Kiat;

    2016-01-01

    developed fuel constituent reduced mechanisms, together with the formerly derived reduced HXN mechanism are comprehensively validated in zero-dimensional chemical kinetic simulations under a wide range of shock tube and jet-stirred reactor (JSR) conditions. Well agreement between the reduced and detailed......In the present work, development and validation of reduced chemical kinetic mechanisms for several different hydrocarbons are performed. These hydrocarbons are potential representative for practical diesel fuel constituents. n-Hexadecane (HXN), 2,2,4,4,6,8,8-heptamethylnonane (HMN), cyclohexane...... (CHX) and toluene are selected to represent straight-alkane, branched-alkane, cyclo-alkane and aromatic compounds in the diesel fuel. A five-stage chemical kinetic mechanism reduction scheme formulated in the previous work is applied to develop the reduced HMN and CHX models based on their respective...

  13. A kinetic and equilibrium analysis of silicon carbide chemical vapor deposition on monofilaments

    Science.gov (United States)

    Gokoglu, S. A.; Kuczmarski, M. A.

    1993-01-01

    Chemical kinetics of atmospheric pressure silicon carbide (SiC) chemical vapor deposition (CVD) from dilute silane and propane source gases in hydrogen is numerically analyzed in a cylindrical upflow reactor designed for CVD on monofilaments. The chemical composition of the SiC deposit is assessed both from the calculated total fluxes of carbon and silicon and from chemical equilibrium considerations for the prevailing temperatures and species concentrations at and along the filament surface. The effects of gas and surface chemistry on the evolution of major gas phase species are considered in the analysis.

  14. Chemical kinetics of flue gas cleaning by electron beam

    International Nuclear Information System (INIS)

    By electron beam treatment of flue gases, NOx and SO2 are converted to nitric and sulfuric acids simultaneously. Upon ammonia addition, the corresponding salts are collected in solid state and can be sold as fertilizer. Both homogeneous gas phase reactions and physico-chemical aerosol dynamics are involved in product formation. These processes have been analyzed by model calculations. In part 1, the present report summarizes the model results and gives an account of the theoretical understanding of the EBDS process and its performance characteristics. Part 2 of this report gives a complete listing of the reactions used in the AGATE code. (orig.)

  15. Development of Kinetic Mechanisms for Next-Generation Fuels and CFD Simulation of Advanced Combustion Engines

    Energy Technology Data Exchange (ETDEWEB)

    Pitz, William J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); McNenly, Matt J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Whitesides, Russell [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Mehl, Marco [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Killingsworth, Nick J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Westbrook, Charles K. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2015-12-17

    Predictive chemical kinetic models are needed to represent next-generation fuel components and their mixtures with conventional gasoline and diesel fuels. These kinetic models will allow the prediction of the effect of alternative fuel blends in CFD simulations of advanced spark-ignition and compression-ignition engines. Enabled by kinetic models, CFD simulations can be used to optimize fuel formulations for advanced combustion engines so that maximum engine efficiency, fossil fuel displacement goals, and low pollutant emission goals can be achieved.

  16. Kinetics and thermodynamics of chemical reactions in Li/SOCl2 cells

    Science.gov (United States)

    Hansen, Lee D.; Frank, Harvey

    1987-01-01

    Work is described that was designed to determine the kinetic constants necessary to extrapolate kinetic data on Li/SOCl2 cells over the temperature range from 25 to 75 C. A second objective was to characterize as far as possible the chemical reactions that occur in the cells since these reactions may be important in understanding the potential hazards of these cells. The kinetics of the corrosion processes in undischarged Li/SOCl2 cells were determined and separated according to their occurrence at the anode and cathode; the effects that switching the current on and off has on the corrosion reactions was determined; and the effects of discharge state on the kinetics of the corrosion process were found. A thermodynamic analysis of the current-producing reactions in the cell was done and is included.

  17. Research in chemical kinetics. Progress report, August 1, 1987--July 20, 1988

    Energy Technology Data Exchange (ETDEWEB)

    Rowland, F.S.

    1996-09-01

    This paper describes chemical kinetics research in the following areas: reactions of thermalized tritium atoms with organo-tin compounds; studies on the hydrolysis of OCS and CS{sub 2}; thermal chlorine 38 reactions with 2,3-dichloro-hexafluoro-2-butene; and thermal T reactions with fluoroethylenes.

  18. Green chemicals : A Kinetic Study on the Conversion of Glucose to Levulinic Acid

    NARCIS (Netherlands)

    Girisuta, B.; Janssen, L.P.B.M.; Heeres, H.J.

    2006-01-01

    Levulinic acid has been identified as a promising green, biomass derived platform chemical. A kinetic study on one of the key steps in the conversion of biomass to levulinic acid, i.e., the acid catalysed decomposition of glucose to levulinic acid has been performed. The experiments were performed i

  19. Chemical kinetics study of hydrocarbon regeneration from organic matter in carbonate source rocks and its significance

    Institute of Scientific and Technical Information of China (English)

    LU ShuangFang; ZHONG NingNing; XUE HaiTao; PAN ChangChun; LI JiJun; LI HongTao

    2007-01-01

    In the comparison research of hydrocarbon regeneration, a low maturity carbonate source rock is heated to different temperatures in a gold tube to obtain a series of samples with different maturities. Then, the heated samples, before and after extraction, are subjected to Rock-Eval pyrolysis through a thermal simulation of hydrocarbon regeneration in order to inspect pyrolysis characteristics and probe into the characteristics of the chemical kinetics of each sample. The results indicate that, whether hydrocarbon regeneration peak is delayed or advanced, the potential of hydrocarbon regeneration is closely related to the expulsion amount and breakdown maturity of primary hydrocarbon generation. After extraction, the average activation energy of artificially maturated samples increases with the in creasing maturity, but the chemical kinetic properties of un-extracted samples decrease. The calibrated chemical kinetic models that describe extracted and un-extracted samples are applied to the Bohai Bay and the Songliao Basin, and the results indicate that the combination of the two models can explain some contradictory conclusions previously reported. These results also facilitate the quantitative evaluation of the amount of hydrocarbon regeneration by the chemical kinetic method.

  20. Kinetic Study of the Chemical Vapor Deposition of Tantalum in Long Narrow Channels

    DEFF Research Database (Denmark)

    Mugabi, James Atwoki; Eriksen, Søren; Petrushina, Irina;

    2016-01-01

    A kinetic study of the chemical vapor deposition of tantalum in long narrow channels is done to optimize the industrial process for the manufacture of tantalum coated plate heat exchangers. The developed model fits well at temperatures between 750 and 850 °C, and in the pressure range of25–990 mbar...

  1. Investigation of Chemical Kinetics on Soot Formation Event of n-Heptane Spray Combustion

    DEFF Research Database (Denmark)

    Pang, Kar Mun; Jangi, Mehdi; Bai, Xue-Song;

    2014-01-01

    In this reported work, 2-dimsensional computational fluid dynamics studies of n-heptane combustion and soot formation processes in the Sandia constant-volume vessel are carried out. The key interest here is to elucidate how the chemical kinetics affects the combustion and soot formation events. N...

  2. An analytical kinetic model for chemical-vapor deposition of pureB layers from diborane

    NARCIS (Netherlands)

    Mohammadi, V.; De Boer, W.B.; Nanver, L.K.

    2012-01-01

    In this paper, an analytical model is established to describe the deposition kinetics and the deposition chamber characteristics that determine the deposition rates of pure boron (PureB-) layers grown by chemical-vapor deposition (CVD) from diborane (B2H6) as gas source on a non-rotating silicon waf

  3. 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

  4. 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...

  5. Cooperative Learning Instruction for Conceptual Change in the Concepts of Chemical Kinetics

    Science.gov (United States)

    Kirik, Ozgecan Tastan; Boz, Yezdan

    2012-01-01

    Learning is a social event and so the students need learning environments that enable them to work with their peers so that they can learn through their interactions. This study discusses the effectiveness of cooperative learning compared to traditional instruction in terms of students' motivation and understanding of chemical kinetics in a high…

  6. The Teaching and Learning of Chemical Kinetics Supported with MS Excel

    Science.gov (United States)

    Zain, Sharifuddin Md; Rahman, Noorsaadah Abdul; Chin, Lee Sui

    2013-01-01

    Students in 12 secondary schools in three states of Malaysia were taught to use worksheets on the chemical kinetics topic which had been pre-created using the MS Excel worksheets. After the teaching, an opinion survey of 612 Form Six students from these schools was conducted. The results showed that almost all the students felt that MS Excel…

  7. Designing and Evaluating an Evidence-Informed Instruction in Chemical Kinetics

    Science.gov (United States)

    Cakmakci, Gultekin; Aydogdu, Cemil

    2011-01-01

    We have investigated the effects of a teaching intervention based on evidence from educational theories and research data, on students' ideas in chemical kinetics. A quasi-experimental design was used to compare the outcomes for the intervention. The subjects of the study were 83 university first-year students, who were in two different classes in…

  8. Chemical kinetics study of hydrocarbon regeneration from organic matter in carbonate source rocks and its significance

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    In the comparison research of hydrocarbon regeneration, a low maturity carbonate source rock is heated to different temperatures in a gold tube to obtain a series of samples with different maturities. Then, the heated samples, before and after extraction, are subjected to Rock-Eval pyrolysis through a thermal simulation of hydrocarbon regeneration in order to inspect pyrolysis characteristics and probe into the characteristics of the chemical kinetics of each sample. The results indicate that, whether hy- drocarbon regeneration peak is delayed or advanced, the potential of hydrocarbon regeneration is closely related to the expulsion amount and breakdown maturity of primary hydrocarbon generation. After extraction, the average activation energy of artificially maturated samples increases with the in- creasing maturity, but the chemical kinetic properties of un-extracted samples decrease. The calibrated chemical kinetic models that describe extracted and un-extracted samples are applied to the Bohai Bay and the Songliao Basin, and the results indicate that the combination of the two models can explain some contradictory conclusions previously reported. These results also facilitate the quantitative evaluation of the amount of hydrocarbon regeneration by the chemical kinetic method.

  9. Chemical mechanical polishing (CMP) of sapphire

    Science.gov (United States)

    Zhu, Honglin

    The concept of chemical mechanical polishing (CMP) was examined for finishing sapphire. In this study sapphire was used as a model system for oxide ceramics. The removal rates were determined by weight loss. Surface quality and structure were characterized with surface probe microscopy (SPM). Polishing experiments were designed to test the chemically modified surface layer. A series of abrasives with various hardnesses including mono-crystalline and polycrystalline diamond, alpha and gamma alumina, zirconia, ceria and silica were used. Diaspore was also evaluated. The results indicated that, with similar particle size and shape, harder abrasives do not necessarily cause faster material removal and better surface finish, and abrasives with hardness equal to or less than sapphire such as alpha alumina and gamma alumina achieved the best surface finish and efficient material removal. A hypothesis was proposed that the sapphire surface was modified by water to form a thin hydration laver with structure and hardness close to diaspore. Abrasives with a hardness between diaspore and sapphire polished the c-plane of sapphire with good surface finish and efficient removal. SPM indicated the hydration layer on the c-plane surface was about 1 nm thick. Removal rate and surface finish as a function of pH were also examined on c-plane sapphire with nano-alumina abrasives. The removal rate as a function of pH was compared to the solubility behavior of alumina. The results showed the deviation of pH from the lowest solubility pH for alumina (pH = 5) was a driving force for the surface reaction to form a hydration layer. The anisotropy of sapphire strongly affects removal rate and surface quality in CMP. The relationships among orientation. pH and abrasive were studied for sapphire with c (0001), a (11-20), and m (10-10) planes. Based on the results, the CMP process for sapphire includes chemical reaction of the surface to form a thin reaction layer that is softer than sapphire

  10. The Utility of the Lambert Function W[a exp(a - bt)] in Chemical Kinetics

    Science.gov (United States)

    Williams, Brian Wesley

    2010-01-01

    The mathematical Lambert function W[a exp(a - bt)] is used to find integrated rate laws for several examples, including simple enzyme and Lindemann-Christiansen-Hinshelwood (LCH) unimolecular decay kinetics. The results derived here for the well-known LCH mechanism as well as for a dimer-monomer reaction mechanism appear to be novel. A nonlinear…

  11. 18F in hot atom chemistry and equilibrium chemical kinetics

    International Nuclear Information System (INIS)

    Superexcited molecules are unusual species that at present can only be investigated using nuclear recoil methods. The thermochemical technique for measuring the excitation energy distributions of superexcited molecules is reviewed and applied to recent studies of CF318F and C2F518F formed from high energy atomic exchange reactions in CF4 and C2F6. The nascent CF318F and C2F518F range in energy from 1.7 to about 45 eV. The average energies of these products range from 15 to 20 eV. The internal excitation that accompanies these reactions is initially localized near the 18F bonding site, and the C2F518F decomposition mechanism is non-statistical. Moderated nuclear recoil experiments yield mechanisms and rates for the reactions of thermal 18F atoms. Under our standard experimental conditions from 3.4 x 104 to 3.4 x 108 labeled product molecules are available for radioassay. This procedure is free from systematic error and the measurements yield exceptional precision and sensitivity because (1) high energy reactions with the thermally active reagents are suppressed. (2) the host environment is rigorously controlled, and (3) the molecular products from many single atom reactions are directly counted. The limitations of this technique are described and results are presented for the reactions of thermal 18F atoms with CH4 and C2H4. (J.P.N.)

  12. Mechanism and kinetics for scavenging superoxide anion by progesterone

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The chemical reaction of progesterone with superoxide anion in 0.1 mol/L NaHCO3 medium is studied by polarography. Differing from the indirect inhibition of generation by synthesized glucocorticoids in mechanism, the function that progesterone scavenges is ascribed to that directly oxidizes the C == C double bond conjugated with the carbonyl moiety of progesterone molecule to a free radical, and then is reduced to H2O2. The result obtained in this work gives new evidence for biomedical research. The equation of rate constant of the oxidization reaction is de-duced, and the apparent rate constant obtained is 308 L·mol-1·s-1.

  13. Learning the mechanisms of chemical disequilibria

    Science.gov (United States)

    Nicholson, Schuyler B.; Alaghemandi, Mohammad; Green, Jason R.

    2016-08-01

    When at equilibrium, large-scale systems obey thermodynamics because they have microscopic configurations that are typical. "Typical" states are a fraction of those possible with the majority of the probability. A more precise definition of typical states underlies the transmission, coding, and compression of information. However, this definition does not apply to natural systems that are transiently away from equilibrium. Here, we introduce a variational measure of typicality and apply it to atomistic simulations of a model for hydrogen oxidation. While a gaseous mixture of hydrogen and oxygen combusts, reactant molecules transform through a variety of ephemeral species en route to the product, water. Out of the exponentially growing number of possible sequences of chemical species, we find that greater than 95% of the probability concentrates in less than 1% of the possible sequences. Overall, these results extend the notion of typicality across the nonequilibrium regime and suggest that typical sequences are a route to learning mechanisms from experimental measurements. They also open up the possibility of constructing ensembles for computing the macroscopic observables of systems out of equilibrium.

  14. Chemical Mechanical Planarization (CMP) for Microelectronic Applications

    Institute of Scientific and Technical Information of China (English)

    Li Yuzhuo

    2004-01-01

    Surface planarity is of paramount importance in microelectronics. Chemical Mechanical Polishing (CMP) is the most viable approach to address the planarity issues during the fabrication of advanced semiconductor devices. With the integration of copper as interconnect and low k materials as dielectric, the CMP community is facing an ever increasing demand on reducing defectivity without scarifying production throughput. Key issues in CMP today include reduction of surface defectivity and enhancement of planarization efficiency. More specifically, the polished surface should be free of defects such as scratches, pits, corrosion spots, and residue particles. To accomplish these goals, we have investigated a wide range of pathways including reduction of oversized particles,use of unique abrasives such as functionalized nanoparticles, and development of polishing solution without abrasive particles.In this presentation, some fundamental aspects of the CMP process will be given first.Several academic and industrial examples will be used to illustrate the issues and challenges during the implementation of various slurry designs into the CMP processes.

  15. Mechanism-based bioanalysis and biomarkers for hepatic chemical stress.

    Science.gov (United States)

    Antoine, D J; Mercer, A E; Williams, D P; Park, B K

    2009-08-01

    Adverse drug reactions, in particular drug-induced hepatotoxicity, represent a major challenge for clinicians and an impediment to safe drug development. Novel blood or urinary biomarkers of chemically-induced hepatic stress also hold great potential to provide information about pathways leading to cell death within tissues. The earlier pre-clinical identification of potential hepatotoxins and non-invasive diagnosis of susceptible patients, prior to overt liver disease is an important goal. Moreover, the identification, validation and qualification of biomarkers that have in vitro, in vivo and clinical transferability can assist bridging studies and accelerate the pace of drug development. Drug-induced chemical stress is a multi-factorial process, the kinetics of the interaction between the hepatotoxin and the cellular macromolecules are crucially important as different biomarkers will appear over time. The sensitivity of the bioanalytical techniques used to detect biological and chemical biomarkers underpins the usefulness of the marker in question. An integrated analysis of the biochemical, molecular and cellular events provides an understanding of biological (host) factors which ultimately determine the balance between xenobiotic detoxification, adaptation and liver injury. The aim of this review is to summarise the potential of novel mechanism-based biomarkers of hepatic stress which provide information to connect the intracellular events (drug metabolism, organelle, cell and whole organ) ultimately leading to tissue damage (apoptosis, necrosis and inflammation). These biomarkers can provide both the means to inform the pharmacologist and chemist with respect to safe drug design, and provide clinicians with valuable tools for patient monitoring. PMID:19621999

  16. LSENS, a general chemical kinetics and sensitivity analysis code for gas-phase reactions: User's guide

    Science.gov (United States)

    Radhakrishnan, Krishnan; Bittker, David A.

    1993-01-01

    A general chemical kinetics and sensitivity analysis code for complex, homogeneous, gas-phase reactions is described. The main features of the code, LSENS, are its flexibility, efficiency and convenience in treating many different chemical reaction models. The models include static system, steady, one-dimensional, inviscid flow, shock initiated reaction, and a perfectly stirred reactor. In addition, equilibrium computations can be performed for several assigned states. An implicit numerical integration method, which works efficiently for the extremes of very fast and very slow reaction, is used for solving the 'stiff' differential equation systems that arise in chemical kinetics. For static reactions, sensitivity coefficients of all dependent variables and their temporal derivatives with respect to the initial values of dependent variables and/or the rate coefficient parameters can be computed. This paper presents descriptions of the code and its usage, and includes several illustrative example problems.

  17. Modeling the Emission of CO from Wood Fires using Detailed Chemical Kinetics

    DEFF Research Database (Denmark)

    Dederichs, Anne

    Carbon monoxide is treated as one of the most common and dangerous of gases evolving in fires. Modeling the formation of the toxic gas CO from in fire enclosures using detailed chemical kinetics is the topic of this manuscript. A semi-empirical model is developed to study the formation of CO from...... birch wood using detailed chemical kinetics on the combustion of pyrolysis gas from birch wood. The composition of the pyrolysis gas is taken from the experiment by Zanzi and coworkers. The numerical model applies a counter flow configuration involving 84 chemical species and 804 reactions. Hence......, the model separately treats the process of pyrolysis and combustion. For under ventilated conditions and at high temperatures during pyrolysis it is found that the process of pyrolysation strongly influences the formation of CO in fire. CO2 follows the same trend....

  18. Colloid Aspects of Chemical-Mechanical Planarization

    Directory of Open Access Journals (Sweden)

    Matijević, E.

    2010-09-01

    Full Text Available The essential parts of interconnects for silicon based logic and memory devices consist of metal wiring (e.g. copper, a barrier metal (Ta, TaN, and of insulation (SiO2 , low-k polymer. The deposition of the conducting metal cannot be confined to trenches, resulting in additional coverage of Cu and Ta/TaN on the surface of the dielectrics, yielding an electrically conducting continuous but an uneven surface. The surplus metal must be removed until a perfectly flat surface consisting of electrically isolated metal lines is achieved with no imperfections. This task is accomplished by the chemical-mechanical planarization (CMP process, in which the wafer is polished with a slurry containing abrasives of finely dispersed particles in submicrometer to nanometer size. The slurries also contain dissolved chemicals to modify the surfaces to be planarized. Eventually the final product must be cleared of any adhered particles and debris left after polishing is completed. Obviously the entire process deals with materials and interactions which are the focal subjects of colloid and surface science, such as the natures of abrasive particles and their stability in the slurry, the properties of various surfaces and their modifications, adhesion and detachment of the particles and different methods for the characterization of constituents, as well as elucidation of the relevant interfacial phenomena. This review endeavors to describe the colloid approach to optimize the materials and processes in order to achieve desirable polish rates and final surfaces with no imperfections. Specifically, the effects of the composition, size, shape, and charge of abrasive particles on the polish process and the quality of planarized wafers is described in detail. Furthermore, the interactions of metal surfaces with oxidizing, chelating, and other species which affect the dissolution and surface modification of metal (copper surfaces are illustrated and related to the

  19. Features in chemical kinetics. II. A self-emerging definition of slow manifolds.

    Science.gov (United States)

    Nicolini, Paolo; Frezzato, Diego

    2013-06-21

    In the preceding paper of this series (Part I [P. Nicolini and D. Frezzato, J. Chem. Phys. 138, 234101 (2013)]) we have unveiled some ubiquitous features encoded in the systems of polynomial differential equations normally applied in the description of homogeneous and isothermal chemical kinetics (mass-action law). Here we proceed by investigating a deeply related feature: the appearance of so-called slow manifolds (SMs) which are low-dimensional hyper-surfaces in the neighborhood of which the slow evolution of the reacting system occurs after an initial fast transient. Indeed a geometrical definition of SM, devoid of subjectivity, "naturally" follows in terms of a specific sub-dimensional domain embedded in the peculiar region of the concentrations phase-space that in Part I we termed as "attractiveness region." Numerical inspections on simple low-dimensional model cases are presented, including the benchmark case of Davis and Skodje [J. Chem. Phys. 111, 859 (1999)] and the preliminary analysis of a simplified model mechanism of hydrogen combustion. PMID:23802946

  20. Transfer of complexed and dissociated ionic species at soft interfaces: a voltammetric study of chemical kinetic and diffusional effects.

    Science.gov (United States)

    Laborda, Eduardo; Olmos, José Manuel; Molina, Ángela

    2016-04-21

    A new transfer mechanism is considered in which two different ionic species of the same charge can be transferred across a soft interface while they interconvert with each other in the original phase through a homogeneous chemical reaction: the aqueous complexation-dissociation coupled to transfer (ACDT) mechanism. This can correspond to a free ion in aqueous solution in the presence of a neutral ligand that complexes it leading to a species that can be more or less lipophilic than the free ion. As a result, the transfer to the organic phase can be facilitated or hindered by the aqueous-phase chemical reaction. Rigorous and approximate explicit analytical solutions are derived for the study of the above mechanism via normal pulse voltammetry, derivative voltammetry and chronoamperometry at macrointerfaces. The solutions enable us to examine the process whatever the species' lipophilicity and diffusivity in each medium and the kinetics and thermodynamics of the chemical reaction in solution. Moreover, when the chemical reaction is at equilibrium, explicit expressions for cyclic voltammetry and square wave voltammetry are obtained. With this set of equations, the influence of different physicochemical phenomena on the voltammetric response is studied as well as the most suitable strategies to characterize them. PMID:27020610

  1. Mechanism and Kinetic Parameters of Thermal Decomposition of Cobalt Dichloride Hexahydrate

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The thermal decomposition of the cobalt dichloride hexahydrate and its kinetics were studied by TG and DTG technique under the non-isothermal condition with nitrogen atnosphere.The non-isothermal kinetic data and kinetic parameters were evaluated by means of integral and differential methods.The most probable mechanism functions of the thermal decomposition reaction for the first stage are:f(α)=(1-α)2 and g(α)=(1-α)-1-1.

  2. The quantum mechanics based on a general kinetic energy

    CERN Document Server

    Wei, Yuchuan

    2016-01-01

    In this paper, we introduce the Schrodinger equation with a general kinetic energy operator. The conservation law is proved and the probability continuity equation is deducted in a general sense. Examples with a Hermitian kinetic energy operator include the standard Schrodinger equation, the relativistic Schrodinger equation, the fractional Schrodinger equation, the Dirac equation, and the deformed Schrodinger equation. We reveal that the Klein-Gordon equation has a hidden non-Hermitian kinetic energy operator. The probability continuity equation with sources indicates that there exists a different way of probability transportation, which is probability teleportation. An average formula is deducted from the relativistic Schrodinger equation, the Dirac equation, and the K-G equation.

  3. Oxidation Kinetics of Chemically Vapor-Deposited Silicon Carbide in Wet Oxygen

    Science.gov (United States)

    Opila, Elizabeth J.

    1994-01-01

    The oxidation kinetics of chemically vapor-deposited SiC in dry oxygen and wet oxygen (P(sub H2O) = 0.1 atm) at temperatures between 1200 C and 1400 C were monitored using thermogravimetric analysis. It was found that in a clean environment, 10% water vapor enhanced the oxidation kinetics of SiC only very slightly compared to rates found in dry oxygen. Oxidation kinetics were examined in terms of the Deal and Grove model for oxidation of silicon. It was found that in an environment containing even small amounts of impurities, such as high-purity Al2O3 reaction tubes containing 200 ppm Na, water vapor enhanced the transport of these impurities to the oxidation sample. Oxidation rates increased under these conditions presumably because of the formation of less protective sodium alumino-silicate scales.

  4. Modeling of Scale-Dependent Bacterial Growth by Chemical Kinetics Approach

    Directory of Open Access Journals (Sweden)

    Haydee Martínez

    2014-01-01

    Full Text Available We applied the so-called chemical kinetics approach to complex bacterial growth patterns that were dependent on the liquid-surface-area-to-volume ratio (SA/V of the bacterial cultures. The kinetic modeling was based on current experimental knowledge in terms of autocatalytic bacterial growth, its inhibition by the metabolite CO2, and the relief of inhibition through the physical escape of the inhibitor. The model quantitatively reproduces kinetic data of SA/V-dependent bacterial growth and can discriminate between differences in the growth dynamics of enteropathogenic E. coli, E. coli  JM83, and Salmonella typhimurium on one hand and Vibrio cholerae on the other hand. Furthermore, the data fitting procedures allowed predictions about the velocities of the involved key processes and the potential behavior in an open-flow bacterial chemostat, revealing an oscillatory approach to the stationary states.

  5. Renormalizing the kinetic energy operator in elementary quantum mechanics

    Energy Technology Data Exchange (ETDEWEB)

    Coutinho, F A B [Faculdade de Medicina, Universidade de Sao Paulo e LIM 01-HCFMUSP, 05405-000 Sao Paulo (Brazil); Amaku, M [Faculdade de Medicina Veterinaria e Zootecnia, Universidade de Sao Paulo, 05508-970 Sao Paulo (Brazil)], E-mail: coutinho@dim.fm.usp.br

    2009-09-15

    In this paper, we consider solutions to the three-dimensional Schroedinger equation of the form {psi}(r) = u(r)/r, where u(0) {ne} 0. The expectation value of the kinetic energy operator for such wavefunctions diverges. We show that it is possible to introduce a potential energy with an expectation value that also diverges, exactly cancelling the kinetic energy divergence. This renormalization procedure produces a self-adjoint Hamiltonian. We solve some problems with this new Hamiltonian to illustrate its usefulness.

  6. Mainz Organics Mechanism (MOM): description and sensitivity to some estimated kinetic parameters

    Science.gov (United States)

    Taraborrelli, Domenico; Cabrera Perez, David; Sander, Rolf; Pozzer, Andrea

    2015-04-01

    Despite decades of reasearch, global atmospheric chemistry models still have significant biases compared to the estimated distribution and evolution of tropospheric ozone and hydroxyl radical. The gas-phase oxidation of volatile organic compounds (VOC) is acknowledged to play an important role among the processes affecting tropospheric ozone, methane lifetime and aerosol evolution. Thus, chemical mechanisms of very diverse complexity have been developed for the major VOCs. However, all mechanisms present shortcomings such as neglection or lumping of intermediates and estimate of many rate constants and product distributions. Here, we present a VOC oxidation mechanism of intermediate complexity called the Mainz Organics Mechanism (MOM). With about 400 species and 1500 reactions, it represents the oxidation of about 20 primarily emitted VOCs comprising small alkanes and alkenes, isoprene, pinenes and monocyclic aromatic compounds. The development protocol significantly borrows from the Master Chemical Mechanism (MCM). However, MOM distinguishes itself for a number of features. First, the structure activity relationship for estimating the rate constants involving hydroxyl radical is site-specific and dependent on temperature. Second, the alkyl nitrate yields are considered to be dependent on temperature, pressure and molecular structure. RO2 + HO2 reaction kinetics is consistent with the recent direct studies of \\chem{OH}-reformation. Isoprene chemistry includes the latest experimental advancements with respect to OH-recycling and alkyl nitrate chemistry. Pinenes chemistry is largely the one by the MCM but with some modifications according to the work of the Leuven's group. Finally, the chemistry of the aromatics is also borrowed from the MCM but with additional photolysis of ortho-nitrophenols leading to \\chem{HONO} formation. The sensitivity of the model to the temperature and pressure dependence of estimated \\chem{OH} rate constants and alkyl nitrate yields will

  7. 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.

  8. Fast Prediction of HCCI and PCCI Combustion with an Artificial Neural Network-Based Chemical Kinetic Model

    Energy Technology Data Exchange (ETDEWEB)

    Piggott, W T; Aceves, S M; Flowers, D L; Chen, J Y

    2007-09-26

    We have added the capability to look at in-cylinder fuel distributions using a previously developed ignition model within a fluid mechanics code (KIVA3V) that uses an artificial neural network (ANN) to predict ignition (The combined code: KIVA3V-ANN). KIVA3V-ANN was originally developed and validated for analysis of Homogeneous Charge Compression Ignition (HCCI) combustion, but it is also applicable to the more difficult problem of Premixed Charge Compression Ignition (PCCI) combustion. PCCI combustion refers to cases where combustion occurs as a nonmixing controlled, chemical kinetics dominated, autoignition process, where the fuel, air, and residual gas mixtures are not necessarily as homogeneous as in HCCI combustion. This paper analyzes the effects of introducing charge non-uniformity into a KIVA3V-ANN simulation. The results are compared to experimental results, as well as simulation results using a more physically representative and computationally intensive code (KIVA3V-MPI-MZ), which links a fluid mechanics code to a multi-zone detailed chemical kinetics solver. The results indicate that KIVA3V-ANN produces reasonable approximations to the more accurate KIVA3V-MPI-MZ at a much reduced computational cost.

  9. Primary Ion Depletion Kinetics (PIDK Studies as a New Tool for Investigating Chemical Ionization Fragmentation Reactions with PTR-MS.

    Directory of Open Access Journals (Sweden)

    Erna Schuhfried

    Full Text Available We report on a new approach for studying fragmentation channels in Proton Transfer Reaction-Mass Spectrometry (PTR-MS, which we name primary ion depletion kinetics (PIDK. PTR-MS is a chemical ionization mass spectrometric (CIMS technique deploying hydronium ions for the chemical ionization. Induced by extremely high concentrations of analyte M, depletion of the primary ions in the drift tube occurs. This is observed as quasi zero concentration of the primary ion H3O(+, and constant MH(+. Under these non-standard conditions, we find an overall changed fragmentation. We offer two explanations. Either the changed fragmentation pattern is the result of secondary proton transfer reactions. Or, alternatively, the fast depletion of H3O(+ leads to reduced heating of H3O(+ in the drift field, and consequently changed fragmentation following protonation of the analyte M. In any case, we use the observed changes in fragmentation as a successful new approach to fragmentation studies, and term it primary ion depletion kinetics, PIDK. PIDK easily yields an abundance of continuous data points with little deviation, because they are obtained in one experimental run, even for low abundant fragments. This is an advantage over traditional internal kinetic energy variation studies (electric field per number density (E/N variation studies. Also, some interpretation on the underlying fragmentation reaction mechanisms can be gleamed. We measure low occurring fragmentation (<2% of MH(+ of the compounds dimethyl sulfide, DMS, a compound that reportedly does not fragment, diethyl sulfide DES, and dipropyl sulfide DPS. And we confirm and complement the results with traditional E/N studies. Summing up, the new approach of primary ion depletion kinetics allows for the identification of dehydrogenation [MH(+ -H2] and adduct formation (RMH(+ as low abundant fragmentation channels in monosulfides.

  10. A Comparison of Kinetic Energy and Momentum in Special Relativity and Classical Mechanics

    Science.gov (United States)

    Riggs, Peter J.

    2016-01-01

    Kinetic energy and momentum are indispensable dynamical quantities in both the special theory of relativity and in classical mechanics. Although momentum and kinetic energy are central to understanding dynamics, the differences between their relativistic and classical notions have not always received adequate treatment in undergraduate teaching.…

  11. Thyroid disrupting chemicals: Mechanisms and mixtures

    Science.gov (United States)

    Environmental contaminants are known to act as thyroid disrupting chemicals (TDCs). Broadly defined, TDCs are xenobiotics that alter the structure or function of the thyroid gland, alter regulatory enzymes associated with thyroid hormone (TH) homeostasis, or change circulating o...

  12. Kinetics and mechanism of soot formation in hydrocarbon combustion

    Science.gov (United States)

    Frenklach, Michael

    1990-01-01

    The focus of this work was on kinetic modeling. The specific objectives were: detailed modeling of soot formation in premixed flames, elucidation of the effects of fuel structure on the pathway to soot, and the development of a numerical technique for accurate modeling of soot particle coagulation and surface growth. Those tasks were successfully completed and are briefly summarized.

  13. Mechanism and kinetics of mineral weathering under acid conditions.

    NARCIS (Netherlands)

    Anbeek, C.

    1994-01-01

    This study deals with the relationships between crystal structure, grain diameter, surface morphology and dissolution kinetics for feldspar and quartz under acid conditions.Intensively ground samples from large, naturally weathered mineral fragments are frequently used in dissolution studies. The su

  14. A Steady-State Approximation to the Two-Dimensional Master Equation for Chemical Kinetics Calculations.

    Science.gov (United States)

    Nguyen, Thanh Lam; Stanton, John F

    2015-07-16

    In the field of chemical kinetics, the solution of a two-dimensional master equation that depends explicitly on both total internal energy (E) and total angular momentum (J) is a challenging problem. In this work, a weak-E/fixed-J collisional model (i.e., weak-collisional internal energy relaxation/free-collisional angular momentum relaxation) is used along with the steady-state approach to solve the resulting (simplified) two-dimensional (E,J)-grained master equation. The corresponding solutions give thermal rate constants and product branching ratios as functions of both temperature and pressure. We also have developed a program that can be used to predict and analyze experimental chemical kinetics results. This expedient technique, when combined with highly accurate potential energy surfaces, is cable of providing results that may be meaningfully compared to experiments. The reaction of singlet oxygen with methane proceeding through vibrationally excited methanol is used as an illustrative example. PMID:25815602

  15. Accelerating finite-rate chemical kinetics with coprocessors: comparing vectorization methods on GPUs, MICs, and CPUs

    CERN Document Server

    Stone, Christopher P

    2016-01-01

    Efficient ordinary differential equation solvers for chemical kinetics must take into account the available thread and instruction-level parallelism of the underlying hardware, especially on many-core coprocessors, as well as the numerical efficiency. A stiff Rosenbrock and nonstiff Runge-Kutta solver are implemented using the single instruction, multiple thread (SIMT) and single instruction, multiple data (SIMD) paradigms with OpenCL. The performances of these parallel implementations were measured with three chemical kinetic models across several multicore and many-core platforms. Two runtime benchmarks were conducted to clearly determine any performance advantage offered by either method: evaluating the right-hand-side source terms in parallel, and integrating a series of constant-pressure homogeneous reactors using the Rosenbrock and Runge-Kutta solvers. The right-hand-side evaluations with SIMD parallelism on the host multicore Xeon CPU and many-core Xeon Phi co-processor performed approximately three ti...

  16. Chemical reduction of complex kinetic models of combustion; Reduction chimique des modeles cinetiques complexes de combustion

    Energy Technology Data Exchange (ETDEWEB)

    Fournet, R.; Glaude, P.A.; Warth, V.; Battin-Leclerc, F.; Scacchi, G.; Come, G.M. [Institut National Polytechnique de Lorraine, Ecole Nationale Superieure des Industries Chimiques, CNRS UMR 7630, INPL ENSIC, Dept. de Chimie Physique des Reacteurs, 54 - Nancy (France)

    2001-07-01

    This paper presents an automatized method allowing to notably reduce the size of the primary mechanism of alkane combustion. The free radicals having the same raw formulation and the same functional groups are presented in a global way as a unique species. In this way, the number of radicals can be divided by a factor of 16 in the case of n-heptane combustion. The kinetic parameters linked with the global mechanism are obtained from a weighted average of the kinetic constants of the detailed mechanism, and this without any adjustment.The simulations performed for the combustion mechanisms of the n-heptane and of a mixture of n-heptane and 2,2,3 trimethyl butane are presented in order to show the validity of the proposed method. (J.S.)

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

    OpenAIRE

    Alves, Giselle M.; Marques Júnior, Wilson; Soares, A. J.; Kremer, Gilberto M.

    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 solution of the Boltzmann equation is determined through an expansion in Sonine polyn...

  18. Edge-controlled growth and kinetics of single-crystal graphene domains by chemical vapor deposition

    OpenAIRE

    Ma, Teng; Ren, Wencai; Zhang, Xiuyun; Liu, Zhibo; Gao, Yang; Yin, Li-Chang; Ma, Xiu-Liang; Ding, Feng; Cheng, Hui-Ming

    2013-01-01

    Controlled synthesis of wafer-sized single crystalline high-quality graphene is a great challenge of graphene growth by chemical vapor deposition because of the complicated kinetics at edges that govern the growth process. Here we report the synthesis of single-crystal graphene domains with tunable edges from zigzag to armchair via a growth–etching–regrowth process. Both growth and etching of graphene are strongly dependent on the edge structure. This growth/etching behavior is well explained...

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

    OpenAIRE

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

    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 can characterize the space of equilibrium points and provide simple dynamical analysis on the state space modulo the space of equilibrium points.

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

    OpenAIRE

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

    2011-01-01

    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 same time the structure of the complex graph and the stoichiometry of the network, and which admits a direct thermodynamical interpretation. This formulation allows us to easily characterize the set ...

  1. Measurement and chemical kinetic model predictions of detonation cell size in methanol-oxygen mixtures

    Science.gov (United States)

    Eaton, R.; Zhang, B.; Bergthorson, J. M.; Ng, H. D.

    2012-03-01

    In this study, detonation cell sizes of methanol-oxygen mixtures are experimentally measured at different initial pressures and compositions. Good agreement is found between the experiment data and predictions based on the chemical length scales obtained from a detailed chemical kinetic model. To assess the detonation sensitivity in methanol-oxygen mixtures, the results are compared with those of hydrogen-oxygen and methane-oxygen mixtures. Based on the cell size comparison, it is shown that methanol-oxygen is more detonation sensitive than methane-oxygen but less sensitive than hydrogen-oxygen.

  2. Chemical Kinetics Study on the Generation Mechanism of Immature to Low-Ma ture Oil and Its Initial Application%未熟—低熟油生成机理的化学动力学研究及其初步应用

    Institute of Scientific and Technical Information of China (English)

    卢双舫; 刘晓艳; 付晓泰; 冯亚丽; 王振平; 薛海涛

    2001-01-01

    that the activation energy of biodegraded amorphous Disower than that of the same type of OM and the activation energy of OM reworked by microbe in labo rator y shows somewhat decrease. This means that the intensive reworking of OM by micr obe is favorable for the early generation of petroleum. The results mentioned ab ove suggested that although the occurrence and enrichment of immature to low mat ure oil may relate to number of different geological conditions or factors, their commonness is that they all have lower activation energy of hydrocarbon genera tion than that of normal OM.   The initial application of the chemical kinetics models shows that the Oms menti oned above do generate a larger amount of hydrocarbons in a burial depth shallower than that of hydrocarbon generation threshold for normal OM. This elucidates quan titatively the generating mechanism of immature to low mature oil existed in various geological conditions. The study of this paper believes that not only it is theoretical credibility, but also practical feasibility to study the generation mechanism of immature to low mature from the theory of chemical kinetics.%对树脂体、木栓质体、可溶有机质、富硫有机质、经细菌强烈改造过的有机质等各类与未熟─低熟油产出密切相关的样品及部分参照样品所进行的系统的化学动力学定量研究显示,虽然未熟─低熟油的产出和富集可能与多种不同的地质条件或因素有关,但它们的共同之处在于这些有机质较常规有机质具有明显偏低的成烃活化能。化学动力学模型的初步应用显示,这些有机质的确能在浅于常规生烃门限的地质条件下开始大量成烃,从而定量阐明了业已报道的各种地质条件下未熟─低熟油产出和富集的机理。

  3. ADSORPTION CHARACTERIZATION OF CO(II IONS ONTO CHEMICALLY TREATED QUERCUS COCCIFERA SHELL: EQUILIBRIUM, KINETIC AND THERMODYNAMIC STUDIES

    Directory of Open Access Journals (Sweden)

    M. Hamdi Karaoglu

    2011-04-01

    Full Text Available Quercus coccifera shell (QCS, a relatively abundant and inexpensive material, is currently being investigated as an adsorbent to remove cobalt(II from water. Before the adsorption experiments, QCS was subjected to chemical treatment to provide maximum surface area. Then, the kinetics and adsorption mechanism of Co(II ions on QCS were studied using different parameters such as adsorbent dosage, initial concentration, temperature, contact time, and solution pH. The loaded metals could be desorbed effectively with dilute hydrochloric acid, nitric acid, and 0.1 M EDTA. The Langmuir and Freundlich models were used to describe the uptake of cobalt on QCS. The equilibrium adsorption data were better fitted to Langmuir adsorption isotherm model. The maximum adsorption capacity (qm of QCS for Co(II was 33 mg g-1. Various kinetic models were used to describe the adsorption process. The adsorption followed pseudo second-order kinetic model. The intraparticle diffusion was found to be the rate-limiting step in the adsorption process. The diffusion coefficients were calculated and found to be in the range of 3.11×10−6 to 168.78×10−6 cm2s-1. The negative DH* value indicated exothermic nature of the adsorption.

  4. Stochastic mechano-chemical kinetics of molecular motors: a multidisciplinary enterprise from a physicist's perspective

    CERN Document Server

    Chowdhury, Debashish

    2013-01-01

    A molecular motor is made of either a single macromolecule or a macromolecular complex. Just like their macroscopic counterparts, molecular motors "transduce" input energy into mechanical work. All the nano-motors considered here operate under isothermal conditions far from equilibrium. Moreover, one of the possible mechanisms of energy transduction, called Brownian ratchet, does not even have any macroscopic counterpart. But, molecular motor is not synonymous with Brownian ratchet; a large number of molecular motors execute a noisy power stroke, rather than operating as Brownian ratchet. We review not only the structural design and stochastic kinetics of individual single motors, but also their coordination, cooperation and competition as well as the assembly of multi-module motors in various intracellular kinetic processes. Although all the motors considered here execute mechanical movements, efficiency and power output are not necessarily good measures of performance of some motors. Among the intracellular...

  5. The Radical Pair Mechanism and the Avian Chemical Compass: Quantum Coherence and Entanglement

    CERN Document Server

    Zhang, Yiteng; Kais, Sabre

    2015-01-01

    We review the spin radical pair mechanism which is a promising explanation of avian navigation. This mechanism is based on the dependence of product yields on (1) the hyperfine interaction involving electron spins and neighboring nuclear spins and (2) the intensity and orientation of the geomagnetic field. One surprising result is that even at ambient conditions quantum entanglement of electron spins can play an important role in avian magnetoreception. This review describes the general scheme of chemical reactions involving radical pairs generated from singlet and triplet precursors; the spin dynamics of the radical pairs; and the magnetic field dependence of product yields caused by the radical pair mechanism. The main part of the review includes a description of the chemical compass in birds. We review: the general properties of the avian compass; the basic scheme of the radical pair mechanism; the reaction kinetics in cryptochrome; quantum coherence and entanglement in the avian compass; and the effects o...

  6. Chemical kinetic pathways for the emission of trace by-products in combustion processes

    International Nuclear Information System (INIS)

    A collorbative research program has been initiated to study the emissions of a wide variety of chemical species from stationary combustion systems. These product species have been included in Clean Air act legislation and their emissions must be rigidly controlled, but there is a need for a much better understanding of the physical and chemical mechanisms that produce and consume them. We are using physical and chemical mechanisms that produce and consume them. We are using numerical modeling techniques to study the chemical reactions and fluid mechanical factors that occur in industrial burners. We are examining systems including premixed and diffusion flames, and stirred and plug flow reactors in these modeling studies to establish the major factors leading to emissions of these chemicals

  7. Calibration of Chemical Kinetic Models Using Simulations of Small-Scale Cookoff Experiments

    Energy Technology Data Exchange (ETDEWEB)

    Wemhoff, A P; Becker, R C; Burnham, A K

    2008-02-26

    Establishing safe handling limits for explosives in elevated temperature environments is a difficult problem that often requires extensive simulation. The largest influence on predicting thermal cookoff safety lies in the chemical kinetic model used in these simulations, and these kinetic model reaction sequences often contain multiple steps. Several small-scale cookoff experiments, notably Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), One-Dimensional Time-to-Explosion (ODTX), and the Scaled Thermal Explosion (STEX) have been performed on various explosives to aid in cookoff behavior determination. Past work has used a single test from this group to create a cookoff model, which does not guarantee agreement with the other experiments. In this study, we update the kinetic parameters of an existing model for the common explosive 2,4,6-Trinitrotoluene (TNT) using DSC and ODTX experimental data at the same time by minimizing a global Figure of Merit based on hydrodynamic simulated data. We then show that the new kinetic model maintains STEX agreement, reduces DSC agreement, and improves ODTX and TGA agreement when compared to the original model. In addition, we describe a means to use implicit hydrodynamic simulations of DSC experiments to develop a reaction model for TNT melting.

  8. An insight into chemical kinetics and turbulence-chemistry interaction modeling in flameless combustion

    Directory of Open Access Journals (Sweden)

    Amir Azimi, Javad Aminian

    2015-01-01

    Full Text Available Computational Fluid Dynamics (CFD study of flameless combustion condition is carried out by solving the Reynolds-Averaged Navier-Stokes (RANS equations in the open-source CFD package of OpenFOAM 2.1.0. Particular attention is devoted to the comparison of three global and detailed chemical mechanisms using the Partially Stirred Reactor (PaSR combustion model for the turbulence-chemistry interaction treatment. The OpenFOAM simulations are assessed against previously published CFD results using the Eddy Dissipation Concept (EDC combustion model as well as the experimental data available in the literature. Results show that global chemical mechanisms provide acceptable predictions of temperature and major species fields in flameless mode with much lower computational costs comparing with the detailed chemical mechanisms. However, incorporation of detailed chemical mechanisms with proper combustion models is crucial to account for finite-rate chemistry effects and accurately predict net production of minor species.

  9. Chemical Kinetics of the TPS and Base Bleeding During Flight Test

    Science.gov (United States)

    Osipov, Viatcheslav; Ponizhovskaya, Ekaterina; Hafiychuck, Halyna; Luchinsky, Dmitry; Smelyanskiy, Vadim; Dagostino, Mark; Canabal, Francisco; Mobley, Brandon L.

    2012-01-01

    The present research deals with thermal degradation of polyurethane foam (PUF) during flight test. Model of thermal decomposition was developed that accounts for polyurethane kinetics parameters extracted from thermogravimetric analyses and radial heat losses to the surrounding environment. The model predicts mass loss of foam, the temperature and kinetic of release of the exhaust gases and char as function of heat and radiation loads. When PUF is heated, urethane bond break into polyol and isocyanate. In the first stage, isocyanate pyrolyses and oxidizes. As a result, the thermo-char and oil droplets (yellow smoke) are released. In the second decomposition stage, pyrolysis and oxidization of liquid polyol occur. Next, the kinetics of chemical compound release and the information about the reactions occurring in the base area are coupled to the CFD simulations of the base flow in a single first stage motor vertically stacked vehicle configuration. The CFD simulations are performed to estimate the contribution of the hot out-gassing, chemical reactions, and char oxidation to the temperature rise of the base flow. The results of simulations are compared with the flight test data.

  10. Gas-Kinetic Navier-Stokes Solver for Hypersonic Flows in Thermal and Chemical Non-Equilibrium Project

    Data.gov (United States)

    National Aeronautics and Space Administration — This SBIR project proposes to develop a gas-kinetic Navier-Stokes solver for simulation of hypersonic flows in thermal and chemical non-equilibrium. The...

  11. PAH growth initiated by propargyl addition: Mechanism development and computational kinetics

    KAUST Repository

    Raj, Abhijeet Dhayal

    2014-04-24

    Polycyclic aromatic hydrocarbon (PAH) growth is known to be the principal pathway to soot formation during fuel combustion, as such, a physical understanding of the PAH growth mechanism is needed to effectively assess, predict, and control soot formation in flames. Although the hydrogen abstraction C2H2 addition (HACA) mechanism is believed to be the main contributor to PAH growth, it has been shown to under-predict some of the experimental data on PAHs and soot concentrations in flames. This article presents a submechanism of PAH growth that is initiated by propargyl (C 3H3) addition onto naphthalene (A2) and the naphthyl radical. C3H3 has been chosen since it is known to be a precursor of benzene in combustion and has appreciable concentrations in flames. This mechanism has been developed up to the formation of pyrene (A4), and the temperature-dependent kinetics of each elementary reaction has been determined using density functional theory (DFT) computations at the B3LYP/6-311++G(d,p) level of theory and transition state theory (TST). H-abstraction, H-addition, H-migration, β-scission, and intramolecular addition reactions have been taken into account. The energy barriers of the two main pathways (H-abstraction and H-addition) were found to be relatively small if not negative, whereas the energy barriers of the other pathways were in the range of (6-89 kcal·mol-1). The rates reported in this study may be extrapolated to larger PAH molecules that have a zigzag site similar to that in naphthalene, and the mechanism presented herein may be used as a complement to the HACA mechanism to improve prediction of PAH and soot formation. © 2014 American Chemical Society.

  12. A model for chemically-induced mechanical loading on MEMS

    DEFF Research Database (Denmark)

    Amiot, Fabien

    2007-01-01

    The development of full displacement field measurements as an alternative to the optical lever technique to measure the mechanical response for microelectro-mechanical systems components in their environment calls for a modeling of chemically-induced mechanical fields (stress, strain, and displac...

  13. Investigation of the chemical and electrochemical phenomena in the chemical mechanical planarization of copper

    Science.gov (United States)

    Wang, Ling

    Chemical mechanical planarization (CMP), a polishing process in which uneven surfaces of a copper film deposited on a wafer are planarized using chemically active slurry containing sub-micron abrasive particles, is key for the metallization of multilevel copper interconnection wires on integrated circuits by damascene processes. The present dissertation study investigates the electrochemical and chemical behavior of copper in aqueous solutions containing chemical reagents representative of those in CMP slurries, and the effects of these chemical constituents, with the aim of improving our understanding of the chemical processes responsible, at least in part, for planarization and material removal in copper CMP, and providing mechanistic and quantitative information for developing comprehensive predictive CMP removal models that incorporate chemical, electrochemical and mechanical factors. In the first part of the dissertation, the passivation behavior of copper in solutions containing hydrogen peroxide and glycine was examined, using various characterization techniques including electrochemical polarization curve measurements, copper coupon exposure tests, and electrochemical quartz crystal microbalance measurements. Polarization curves were measured with a rotating disk copper electrode in glycine solution, in the presence and absence of hydrogen peroxide, to understand the role of hydrogen peroxide in the oxidative dissolution and passivation of copper. Weight loss and copper solubilization measurements were conducted by exposing copper coupons to glycine solutions containing hydrogen peroxide, with various concentrations, at different solution pHs, to characterize the development and degree of the peroxide-induced passivation of copper and to obtain the kinetics of copper dissolution, in order to gain insight into the passivation mechanisms of copper in the peroxide-glycine-based solutions. The Quartz Crystal Microbalance (QCM) measurements were conducted with

  14. Kinetic Ballooning Instability as a Substorm Onset Mechanism

    International Nuclear Information System (INIS)

    A new scenario of substorm onset and current disruption and the corresponding physical processes are presented based on the AMPTE/CCE spacecraft observation and a kinetic ballooning instability theory. During the growth phase of substorms the plasma beta is larger than unity (20 greater than or equal to beta greater than or equal to 1). Toward the end of the late growth phase the plasma beta increases from 20 to greater than or equal to 50 in approximately 3 minutes and a low-frequency instability with a wave period of 50 - 75 sec is excited and grows exponentially to a large amplitude at the current disruption onset. At the onset, higher-frequency instabilities are excited so that the plasma and electromagnetic field form a turbulent state. Plasma transport takes place to modify the ambient pressure profile so that the ambient magnetic field recovers from a tail-like geometry to a dipole-like geometry. A kinetic ballooning instability (KBI) theory is proposed to explain the low-frequency instability (frequency and growth rate) and its observed high beta threshold (beta subscript c is greater than or equal to 50). Based on the ideal-MHD theory beta subscript c, superscript MHD approximately equals 1 and the ballooning modes are predicted to be unstable during the growth phase, which is inconsistent with observation that no appreciable magnetic field fluctuation is observed. The enhancement beta subscript c over beta subscript c, superscript MHD is due to the kinetic effects of trapped electrons and finite ion-Larmor radii which provide a large stabilizing effect by producing a large parallel electric field and hence a parallel current that greatly enhances the stabilizing effect of field line tension. As a result, beta subscript c is greatly increased over beta subscript c, superscript MHD by a factor proportional to the ratio of the total electron density to the untrapped electron density (n subscript e divided by n subscript eu) which is greater than or equal to

  15. Transfer Kinetics at the Aqueous/Non-Aqueous Phase Liquid Interface. A Statistical Mechanic Approach

    Science.gov (United States)

    Doss, S. K.; Ezzedine, S.; Ezzedine, S.; Ziagos, J. P.; Hoffman, F.; Gelinas, R. J.

    2001-05-01

    Many modeling efforts in the literature use a first-order, linear-driving-force model to represent the chemical dissolution process at the non-aqueous/aqueous phase liquid (NAPL/APL) interface. In other words, NAPL to APL phase flux is assumed to be equal to the difference between the solubility limit and the "bulk aqueous solution" concentrations times a mass transfer coefficient. Under such assumptions, a few questions are raised: where, in relation to a region of pure NAPL, does the "bulk aqueous solution" regime begin and how does it behave? The answers are assumed to be associated with an arbitrary, predetermined boundary layer, which separates the NAPL from the surrounding solution. The mass transfer rate is considered to be, primarily, limited by diffusion of the component through the boundary layer. In fact, compositional models of interphase mass transfer usually assume that a local equilibrium is reached between phases. Representing mass flux as a rate-limiting process is equivalent to assuming diffusion through a stationary boundary layer with an instantaneous local equilibrium and linear concentration profile. Some environmental researchers have enjoyed success explaining their data using chemical engineering-based correlations. Correlations are strongly dependent on the experimental conditions employed. A universally applicable theory for NAPL dissolution in natural systems does not exist. These correlations are usually expressed in terms of the modified Sherwood number as a function of Reynolds, Peclet, and Schmidt numbers. The Sherwood number may be interpreted as the ratio between the grain size and the thickness of the Nernst stagnant film. In the present study, we show that transfer kinetics at the NAPL/APL interface under equilibrium conditions disagree with approaches based on the Nernst stagnant film concept. It is unclear whether local equilibrium assumptions used in current models are suitable for all situations.A statistical mechanic

  16. Thermochemical analysis and kinetics aspects for a chemical model for camphene ozonolysis.

    Science.gov (United States)

    Oliveira, R C de M; Bauerfeldt, G F

    2012-10-01

    In this work, a chemical model for the camphene ozonolysis, leading to carbonyl final products, is proposed and discussed on the basis of the thermochemical properties and kinetic data obtained at density functional theory levels of calculation. The mechanism is initiated by the electrophilic attack of ozone to the double bond in camphene leading to a 1,2,3-trioxolane intermediate, which decomposes to peroxy radicals and carbonyl compounds in a total of 10 elementary reactions. The thermodynamic properties (enthalpy and entropies differences) are calculated at 298 K. For the thermochemical evaluation, theoretical calculations are performed with the B3LYP, MPW1PW91, and mPW1K density functionals and the basis sets 6-31G(d), 6-31G(2d,2p), 6-31+G(d,p), and 6-31+G(2d,2p). Eventually, single point calculations adopting the 6-311++G(2d,2p) basis set are performed in order to improve the electronic energies. The enthalpy profiles suggest highly exothermic reactions for the individual steps, with a global enthalpy difference of -179.18 kcal mol(-1), determined at the B3LYP∕6-31+G(2d,2p) level. The Gibbs free energy differences for each step, at 298 K, calculated at the B3LYP∕6-311++G(2d,2p)∕∕B3LYP∕6-31+G(2d,2p) level, are used to estimate the composition of a final product mixture under equilibrium conditions as 58% of camphenilone and 42% of 6,6-dimethyl-ɛ-caprolactone-2,5-methylene. For the reaction kinetics, the bimolecular O(3) + camphene step is assumed to be rate determining in the global mechanism. A saddle point for the ozone addition to the double bond is located and rate constants are determined on the basis of the transition state theory. This saddle point is well represented by a loosely bound structure and corrections for the basis set superposition error (BSSE) are calculated, either by considering the effect over the geometry optimization procedure (here referred as CP1 procedure), or the effect of the BSSE over the electronic energy of a

  17. Performance enhancement of zero valent iron based systems using depassivators: Optimization and kinetic mechanisms.

    Science.gov (United States)

    Ansaf, Karim Vayalunkal Karottu; Ambika, Selvaraj; Nambi, Indumathi Manivannan

    2016-10-01

    The long-term ability of Zero-Valent Iron (ZVI) in contaminant removal relies on the effectiveness of iron to serve as electron donor, which makes it a versatile remediation material. However, the formation of oxide and hydroxide layers results in passive layer on ZVI surface during contaminant removal hinders its reactivity. The focus of this research was to evaluate the performance of corrosive agents such as acetic acid (HAc), aluminium sulphate (Alum) and potassium chloride (KCl) as depassivators to overcome passivation for sustainability and longevity. Batch experiments using seven combinations of the above chemicals were conducted to optimize the dosage of depassivators based on passive layer removal. The influence of depassivators in catalytic activity of ZVI in removing Cr(6+) was evaluated. The passive layer on ZVI particles was characterized using Scanning Electron Microscopy (SEM) and confirmed by Energy-Dispersive X-ray spectroscopy (EDAX) analysis. The major mechanisms in passive layer removal was found to be H(+) ion embrittlement followed by uniform depassivation when [HAc] was used and pitting corrosion when [Alum] and [KCl]were used. All the seven sets of chemicals enabled depassivation, but considering the criteria of maximum depassivation, catalytic activity and long term reactivity the depassivation treatments were effective in order as [HAc-Alum] > [HAc-Alum-KCl] >[HAc] > [Alum] > [HAc-KCl] > [KCl] > [Alum-KCl]. The kinetic rate of ZVI using [HAc-Alum] and [Alum] was relatively unchanged over the pH range of 4-10, made it suitable for ex-situ remediation. This insignificant influence of initial pH in catalytic activity of ZVI along with the improvement in longevity and sustainability makes it suitable for effective water treatment applications. The present work has successfully demonstrated that chemical depassivation can restore considerable reactivity of ZVI in the existing permeable reactive barriers. PMID:27395028

  18. Kinetics and mechanism of the oxidation of formic and oxalic acids by quinolinium fluorochromate

    Indian Academy of Sciences (India)

    Madhu Khurana; Pradeep K Sharma; Kalyan K Banerji

    2000-04-01

    Kinetics and mechanism of oxidation of formic and oxalic acids by quinolinium fluorochromate (QFC) have been studied in dimethylsulphoxide. The main product of oxidation is carbon dioxide. The reaction is first-order with respect to QFC. Michaelis-Menten type of kinetics were observed with respect to the reductants. The reaction is acid-catalysed and the acid dependence has the form: obs = + [H+]. The oxidation of -deuterioformic acid exhibits a substantial primary kinetic isotope effect (H/D = 6.01 at 303 K). The reaction has been studied in nineteen different organic solvents and the solvent effect has been analysed using Taft’s and Swain’s multiparametric equations. The temperature dependence of the kinetic isotope effect indicates the presence of a symmetrical cyclic transition state in the rate-determining step. Suitable mechanisms have been proposed

  19. Kinetics and Reaction Mechanisms of High-Temperature Flash Oxidation of Molybdenite

    Science.gov (United States)

    Wilkomirsky, Igor; Otero, Alfonso; Balladares, Eduardo

    2010-02-01

    The kinetics and reaction mechanism of the flash oxidation of +35/-53 μm molybdenite particles in air, as well as in 25, 50, and 100 pct oxygen higher than 800 K, has been investigated using a stagnant gas reactor and a laminar flow reactor coupled to a fast-response, two-wavelength pyrometer. The changes in the morphology and in the chemical composition of partially reacted particles were also investigated by scanning electron microscopy (SEM), X-ray diffraction (XRD), differential thermal analysis (DTA), and electron microprobe. High-speed photography was also used to characterize the particle combustion phenomena. The effects of oxygen concentration and gas temperature on ignition and peak combustion temperatures were studied. The experimental results indicate that MoS2 goes through a process of ignition/combustion with the formation of gaseous MoO3 and SO2 with no evidence of formation of a molten phase, although the reacting molybdenite particles reach temperatures much higher than their melting temperature. This effect may be a result of the combustion of gaseous sulfur from partial decomposition of molybdenite to Mo2S3 under a high gas temperature and 100 pct oxygen. In some cases, the partial fragmentation and distortion of particles also takes place. The transformation can be approximated to the unreacted core model with chemical control and with activation energy of 104.0 ± 4 kJ/mol at the actual temperature of the reacting particles. The reaction was found to be first order with respect to the oxygen concentration. The rate constant calculated at the actual temperatures of the reacting particles shows a good agreement with kinetic data obtained at lower temperatures. The ignition temperature of molybdenite shows an inverse relationship with the gas temperature and oxygen content, with the lowest ignition temperature of 1120 K for 100 pct oxygen. Increasing the oxygen content from 21 to 100 pct increases the particle combustion temperature from 1600 K

  20. A comprehensive experimental and detailed chemical kinetic modelling study of 2,5-dimethylfuran pyrolysis and oxidation.

    Science.gov (United States)

    Somers, Kieran P; Simmie, John M; Gillespie, Fiona; Conroy, Christine; Black, Gráinne; Metcalfe, Wayne K; Battin-Leclerc, Frédérique; Dirrenberger, Patricia; Herbinet, Olivier; Glaude, Pierre-Alexandre; Dagaut, Philippe; Togbé, Casimir; Yasunaga, Kenji; Fernandes, Ravi X; Lee, Changyoul; Tripathi, Rupali; Curran, Henry J

    2013-11-01

    The pyrolytic and oxidative behaviour of the biofuel 2,5-dimethylfuran (25DMF) has been studied in a range of experimental facilities in order to investigate the relatively unexplored combustion chemistry of the title species and to provide combustor relevant experimental data. The pyrolysis of 25DMF has been re-investigated in a shock tube using the single-pulse method for mixtures of 3% 25DMF in argon, at temperatures from 1200-1350 K, pressures from 2-2.5 atm and residence times of approximately 2 ms. Ignition delay times for mixtures of 0.75% 25DMF in argon have been measured at atmospheric pressure, temperatures of 1350-1800 K at equivalence ratios (ϕ) of 0.5, 1.0 and 2.0 along with auto-ignition measurements for stoichiometric fuel in air mixtures of 25DMF at 20 and 80 bar, from 820-1210 K. This is supplemented with an oxidative speciation study of 25DMF in a jet-stirred reactor (JSR) from 770-1220 K, at 10.0 atm, residence times of 0.7 s and at ϕ = 0.5, 1.0 and 2.0. Laminar burning velocities for 25DMF-air mixtures have been measured using the heat-flux method at unburnt gas temperatures of 298 and 358 K, at atmospheric pressure from ϕ = 0.6-1.6. These laminar burning velocity measurements highlight inconsistencies in the current literature data and provide a validation target for kinetic mechanisms. A detailed chemical kinetic mechanism containing 2768 reactions and 545 species has been simultaneously developed to describe the combustion of 25DMF under the experimental conditions described above. Numerical modelling results based on the mechanism can accurately reproduce the majority of experimental data. At high temperatures, a hydrogen atom transfer reaction is found to be the dominant unimolecular decomposition pathway of 25DMF. The reactions of hydrogen atom with the fuel are also found to be important in predicting pyrolysis and ignition delay time experiments. Numerous proposals are made on the mechanism and kinetics of the previously unexplored

  1. Kinematic and Kinetic Analysis for the Tilting Mechanism of Railway Passenger Cars

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The kinematics and kinetics of the tilting mechanism of railway passenger cars are studied. The parameters of the mechanism are given. The motions of the actuator, the center of gravity of the carbody and the center of coupler are calculated. Finally, the maximum driving force, output power and velocity of the actuator are discussed in detail.

  2. 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

  3. 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. PMID:27147197

  4. Effect of mechanical stress on biofilms challenged by different chemicals.

    Science.gov (United States)

    Simões, Manuel; Pereira, Maria Olivia; Vieira, Maria João

    2005-12-01

    In this study a methodology was applied in order to ascertain the mechanical stability of biofilms, by using a stainless-steel (SS) rotating device immersed in a biological reactor where biofilms formed by Pseudomonas fluorescens were allowed to grow for 7 days at a Reynolds number of agitation of 2400. The biofilms developed with this system were characterised in terms of amount of total, extracellular and intracellular proteins and polysaccharides, amount of mass, metabolic activity and mechanical stability, showing that the biofilms were active, had a high content of extracellular constituents and an inherent mechanical stability. In order to assess the role of chemical agents on the mechanical stability, the biofilms were exposed to chemical agents followed by mechanical treatments by submission to increase Reynolds number of agitation. Seven different chemical agents were tested (two non-oxidising biocides, three surfactants and two oxidising biocides) and their effects on the biofilm mechanical stability were evaluated. The increase in the Reynolds number increased the biofilm removal, but total biofilm removal was not found for all the conditions tested. For the experiment without chemical addition (only mechanical treatment), the biofilm remaining on the surface was about 76%. The chemical treatment followed by the subsequent mechanical treatment did not remove all the biofilms from the surface. The biofilm remaining on the SS cylinder ranged from 3% to 62%, depending on the chemical treatment, showing that the chemical treatment is far from being a cause that induces massive biofilm detachment and even the synergistic chemical and mechanical treatments did not promote biofilm removal. Some chemical agents promoted an increase in the biofilm mechanical stability such as glutaraldehyde (GTA), benzalkonium chloride (BC), except for the lower concentration tested, and sodium dodecyl sulphate (SDS), except for the higher concentration tested. Treatments that

  5. Chemical kinetic study of the oxidation of toluene and related cyclic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Mehl, M; Frassoldati, A; Fietzek, R; Faravelli, T; Pitz, W; Ranzi, E

    2009-10-01

    Chemical kinetic models of hydrocarbons found in transportation fuels are needed to simulate combustion in engines and to improve engine performance. The study of the combustion of practical fuels, however, has to deal with their complex compositions, which generally involve hundreds of compounds. To provide a simplified approach for practical fuels, surrogate fuels including few relevant components are used instead of including all components. Among those components, toluene, the simplest of the alkyl benzenes, is one of the most prevalent aromatic compounds in gasoline in the U.S. (up to 30%) and is a promising candidate for formulating gasoline surrogates. Unfortunately, even though the combustion of aromatics been studied for a long time, the oxidation processes relevant to this class of compounds are still matter of discussion. In this work, the combustion of toluene is systematically approached through the analysis of the kinetics of some important intermediates contained in its kinetic submechanism. After discussing the combustion chemistry of cyclopentadiene, benzene, phenol and, finally, of toluene, the model is validated against literature experimental data over a wide range of operating conditions.

  6. Effects of correlated parameters and uncertainty in electronic-structure-based chemical kinetic modelling

    Science.gov (United States)

    Sutton, Jonathan E.; Guo, Wei; Katsoulakis, Markos A.; Vlachos, Dionisios G.

    2016-04-01

    Kinetic models based on first principles are becoming common place in heterogeneous catalysis because of their ability to interpret experimental data, identify the rate-controlling step, guide experiments and predict novel materials. To overcome the tremendous computational cost of estimating parameters of complex networks on metal catalysts, approximate quantum mechanical calculations are employed that render models potentially inaccurate. Here, by introducing correlative global sensitivity analysis and uncertainty quantification, we show that neglecting correlations in the energies of species and reactions can lead to an incorrect identification of influential parameters and key reaction intermediates and reactions. We rationalize why models often underpredict reaction rates and show that, despite the uncertainty being large, the method can, in conjunction with experimental data, identify influential missing reaction pathways and provide insights into the catalyst active site and the kinetic reliability of a model. The method is demonstrated in ethanol steam reforming for hydrogen production for fuel cells.

  7. 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.

  8. Students' Misconceptions about Heat Transfer Mechanisms and Elementary Kinetic Theory

    Science.gov (United States)

    Pathare, S. R.; Pradhan, H. C.

    2010-01-01

    Heat and thermodynamics is a conceptually rich area of undergraduate physics. In the Indian context in particular there has been little work done in this area from the point of view of misconceptions. This prompted us to undertake a study in this area. We present a study of students' misconceptions about heat transfer mechanisms, i.e. conduction,…

  9. Kinetic process of mechanical alloying in Fe50Cu50

    DEFF Research Database (Denmark)

    Huang, J.Y.; Jiang, Jianzhong; Yasuda, H.;

    1998-01-01

    It is shown that mechanical alloying in the immiscible Fe-Cu system is governed by the atomic shear event and shear-induced diffusion process. We found that an alpha-to-gamma phase transformation, as evidenced by the Nishiyama-Wasserman orientation relationship, occurs by simultaneous shearing...

  10. Kinetic and thermodynamic studies on biosorption of Cu(Ⅱ) by chemically modified orange peel

    Institute of Scientific and Technical Information of China (English)

    FENG Ning-chuan; GUO Xue-yi; LIANG Sha

    2009-01-01

    Cu(H) biosorption by orange peel that was chemically modified with sodium hydroxide and calcium chloride was investigated. The effects of temperature, contact time, initial concentration of metal ions and pH on the biosorption of Cu( II) ions were assessed. Thermodynamic parameters including change of free energy(△G~Θ), enthalpy (△H~Θ) and entropy(△S~Θ) during the biosorption were determined. The results show that the biosorption process of Cu( II) ions by chemically treated orange peel is feasible, spontaneous and exothermic under studied conditions. Equilibrium is well described by Langmuir equation with the maximum biosorption capacity(q_m) for Cu( II) as 72.73 mg/g and kinetics is found to fit pseudo-second order type biosorption kinetics. As the temperature increases from 16 ℃ to 60 ℃, copper biosorption decreases. The loaded biosorbent is regenerated using HC1 solution for repeatedly use for five times with little loss of biosorption capacity.

  11. Chemical kinetic analysis of hydrogen-air ignition and reaction times

    Science.gov (United States)

    Rogers, R. C.; Schexnayder, C. J., Jr.

    1981-01-01

    An anaytical study of hydrogen air kinetics was performed. Calculations were made over a range of pressure from 0.2 to 4.0 atm, temperatures from 850 to 2000 K, and mixture equivalence ratios from 0.2 to 2.0. The finite rate chemistry model included 60 reactions in 20 species of the H2-O2-N2 system. The calculations also included an assessment of how small amounts of the chemicals H2O, NOx, H2O2, and O3 in the initial mixture affect ignition and reaction times, and how the variation of the third body efficiency of H2O relative of N2 in certain key reactions may affect reaction time. The results indicate that for mixture equivalence ratios between 0.5 and 1.7, ignition times are nearly constant; however, the presence of H2O and NO can have significant effects on ignition times, depending on the mixture temperature. Reaction time is dominantly influenced by pressure but is nearly independent of initial temperature, equivalence ratio, and the addition of chemicals. Effects of kinetics on reaction at supersonic combustor conditions are discussed.

  12. Do arbuscular mycorrhizal fungi affect cadmium uptake kinetics, subcellular distribution and chemical forms in rice?

    Science.gov (United States)

    Li, Hui; Luo, Na; Zhang, Li Jun; Zhao, Hai Ming; Li, Yan Wen; Cai, Quan Ying; Wong, Ming Hung; Mo, Ce Hui

    2016-11-15

    Rice (Oryza sativa L.) plants were inoculated with two species of arbuscular mycorrhizal fungi (AMF) - Rhizophagus intraradices (RI) and Funneliformis mosseae (FM) and grown for 60days to ensure strong colonization. Subsequently, a short-term hydroponic experiment was carried out to investigate the effects of AMF on cadmium (Cd) uptake kinetics, subcellular distribution and chemical forms in rice exposed to six Cd levels (0, 0.005, 0.01, 0.025, 0.05, 0.1mM) for three days. The results showed that the uptake kinetics of Cd fitted the Michaelis-Menten model well (R(2)>0.89). AMF significantly decreased the Cd concentrations both in shoots and roots in Cd solutions. Furthermore, the decrement of Cd concentrations by FM was significantly higher than RI treatment in roots. AMF reduced the Cd concentrations markedly in the cell wall fractions at high Cd substrate (≥0.025mM). The main subcellular fraction contributed to Cd detoxification was cell wall at low Cd substrate (AMF colonization at high Cd substrate (≥0.05mM), both in shoots and roots. This suggested that AMF could convert Cd into inactive forms which were less toxic. Therefore, AMF could enhance rice resistance to Cd through altering subcellular distribution and chemical forms of Cd in rice. PMID:27450963

  13. Kinetics and mechanism of hexavalent chromium removal by basic oxygen furnace slag.

    Science.gov (United States)

    Han, Chong; Jiao, Yanan; Wu, Qianqian; Yang, Wangjin; Yang, He; Xue, Xiangxin

    2016-08-01

    Basic oxygen furnace slag (BOFS) has the potential to remove hexavalent chromium (Cr(VI)) from wastewater by a redox process due to the presence of minerals containing Fe(2+). The effects of the solution pH, initial Cr(VI) concentration, BOFS dosage, BOFS particle size, and temperature on the removal of Cr(VI) was investigated in detail through batch tests. The chemical and mineral compositions of fresh and reacted BOFS were characterized using scanning electron microscope (SEM) equipped with an energy dispersive spectrometer (EDS) system and X-ray diffractometer (XRD). The results show that Cr(VI) in wastewater can be efficiently removed by Fe(2+) released from BOFS under appropriate acidic conditions. The removal of Cr(VI) by BOFS significantly depended on the parameters mentioned above. The reaction of Cr(VI) with BOFS followed the pseudo-second-order kinetic model. Fe(2+) responsible for Cr(VI) removal was primarily derived from the dissolution of FeO and Fe3O4 in BOFS. When H2SO4 was used to adjust the solution acidity, gypsum (CaSO4·2H2O) could be formed and become an armoring precipitate layer on the BOFS surface, hindering the release of Fe(2+) and the removal of Cr(VI). Finally, the main mechanism of Cr(VI) removal by BOFS was described using several consecutive reaction steps. PMID:27521937

  14. Solid state amorphization kinetic of alpha lactose upon mechanical milling.

    Science.gov (United States)

    Caron, Vincent; Willart, Jean-François; Lefort, Ronan; Derollez, Patrick; Danède, Florence; Descamps, Marc

    2011-11-29

    It has been previously reported that α-lactose could be totally amorphized by ball milling. In this paper we report a detailed investigation of the structural and microstructural changes by which this solid state amorphization takes place. The investigations have been performed by Powder X-ray Diffraction, Solid State Nuclear Magnetic Resonance ((13)C CP-MAS) and Differential Scanning Calorimetry. The results reveal the structural complexity of the material in the course of its amorphization so that it cannot be considered as a simple mixture made of a decreasing crystalline fraction and an increasing amorphous fraction. Heating this complexity can give rise to a fully nano-crystalline material. The results also show that chemical degradations upon heating are strongly connected to the melting process. PMID:21983262

  15. Reaction Kinetics and Mechanism of Magnetic Field Effects in Cryptochrome

    OpenAIRE

    Ilia A Solov'yov; Schulten, Klaus

    2012-01-01

    Creatures as varied as mammals, fish, insects, reptiles, and birds have an intriguing ‘sixth’ sense that allows them to orient themselves in the Earth's magnetic field. Despite decades of study, the physical basis of this magnetic sense remains elusive. A likely mechanism is furnished by magnetically sensitive radical pair reactions occurring in the retina, the light-sensitive part of animal eyes. A photoreceptor, cryptochrome, has been suggested to endow birds with magnetoreceptive abilities...

  16. Kinetics and mechanism of removal of methylene blue by adsorption onto perlite.

    Science.gov (United States)

    Doğan, Mehmet; Alkan, Mahir; Türkyilmaz, Aydin; Ozdemir, Yasemin

    2004-06-18

    The kinetics and mechanism of methylene blue adsorption on perlite have been studied. The effects of various experimental parameters, such as initial dye concentration, temperature and pH on the adsorption rate were investigated. Adsorption measurements show that the process is very fast and physical in nature. The extent of the dye removal increased with increase in the initial concentration of the dye and the initial pH and temperature of solution. Adsorption data were modelled using the first and second-order kinetic equations, mass transfer and intra-particle diffusion models. It was shown that the second-order kinetic equation could best describe the sorption kinetics. The diffusion coefficient, D, was found to increase when the initial dye concentration, pH and temperature were raised. Thermodynamic activation parameters, such as DeltaG*, DeltaS* and DeltaH*, were calculated.

  17. Kinetics and mechanism of the adsorption of methylene blue onto ACFs

    Institute of Scientific and Technical Information of China (English)

    YANG Zhi-yuan

    2008-01-01

    The kinetics and mechanism of methylene blue (MB) adsorption onto activated carbon fibers (ACFs) have been studied.The effects of various experimental parameters, such as the initial MB concentration and the ACF mass, on the adsorption rate were investigated. Equilibrium data were fit well by a Freundlich isotherm equation. Adsorption measurements show that the process is very fast. The adsorption data were modeled using first- and second-order kinetic equations and intra-particle diffusion models. It was found that the first-order kinetic equation could best describe the adsorption kinetics. The adsorption process was found to be complex and controlled by both surface and pore diffusion with surface diffusion at the earlier stages, followed by pore diffusion at the later stages. The thermodynamic parameters △G0, △S0 and △H0, have been calculated. The thermodynamics of the MB-ACF system indicate that the adsorption process is spontaneous.

  18. Reaction kinetics and mechanism of magnetic field effects in cryptochrome

    DEFF Research Database (Denmark)

    Solov'yov, Ilia; Schulten, Klaus

    2012-01-01

    Creatures as varied as mammals, fish, insects, reptiles, and birds have an intriguing sixth sense that allows them to orient themselves in the Earth's magnetic field. Despite decades of study, the physical basis of this magnetic sense remains elusive. A likely mechanism is furnished by magnetically...... absorption and electron-spin-resonance observations together with known facts on avian magnetoreception. The reaction cycle permits one to predict magnetic field effects on cryptochrome activation and deactivation. The suggested analysis method gives insight into structural and dynamic design features...... required for optimal detection of the geomagnetic field by cryptochrome and suggests further experimental and theoretical studies....

  19. Sample Handling and Chemical Kinetics in an Acoustically Levitated Drop Microreactor

    Science.gov (United States)

    2009-01-01

    Accurate measurement of enzyme kinetics is an essential part of understanding the mechanisms of biochemical reactions. The typical means of studying such systems use stirred cuvettes, stopped-flow apparatus, microfluidic systems, or other small sample containers. These methods may prove to be problematic if reactants or products adsorb to or react with the container’s surface. As an alternative approach, we have developed an acoustically-levitated drop reactor eventually intended to study enzyme-catalyzed reaction kinetics related to free radical and oxidative stress chemistry. Microliter-scale droplet generation, reactant introduction, maintenance, and fluid removal are all important aspects in conducting reactions in a levitated drop. A three capillary bundle system has been developed to address these needs. We report kinetic measurements for both luminol chemiluminescence and the reaction of pyruvate with nicotinamide adenine dinucleotide, catalyzed by lactate dehydrogenase, to demonstrate the feasibility of using a levitated drop in conjunction with the developed capillary sample handling system as a microreactor. PMID:19769373

  20. Ordens não inteiras em cinética química Non-integer orders in chemical kinetics

    Directory of Open Access Journals (Sweden)

    André P. Oliveira

    2010-01-01

    Full Text Available Starting from zero-, first-, and second-order integrated laws for chemical kinetics, some cases are shown which produce fractional orders. Taking the Michaelis-Menten mechanism as a first example, it is shown that substrate order can go from 1 to zero, depending on relative concentration of enzyme and substrate. Using other examples which show fractional orders higher than one and even negative (inhibition, it is shown that the presence of an equilibrium before or parallel to the rate determining step can be the reason for fractional orders, which is an indication of a more complex mechanism.

  1. Kinetics and mechanism of the mercury(II)-assisted hydrolysis of methyl iodide.

    Science.gov (United States)

    Celo, Valbona; Scott, Susannah L

    2005-04-01

    The kinetics and mechanism of the reaction of aqueous Hg(II) with methyl iodide have been investigated. The overall reaction is best described as Hg(II)-assisted hydrolysis, resulting in quantitative formation of methanol and, in the presence of excess methyl iodide, ultimately, HgI2 via the intermediate HgI+. The kinetics are biexponential when methyl iodide is in excess. At 25 degrees C, the acceleration provided by Hg2+ is 7.5 times greater than that caused by HgI+, while assistance of hydrolysis was not observed for HgI2. Thus, the reactions are not catalytic in Hg(II). The kinetics are consistent with an SN2-M+ mechanism involving electrophilic attack at iodide. As expected, methylation of mercury is not a reaction pathway; traces of methylmercury(II) are artifacts of the extraction/preconcentration procedure used for methylmercury analysis.

  2. Molecular mechanisms of protein aggregation from global fitting of kinetic models.

    Science.gov (United States)

    Meisl, Georg; Kirkegaard, Julius B; Arosio, Paolo; Michaels, Thomas C T; Vendruscolo, Michele; Dobson, Christopher M; Linse, Sara; Knowles, Tuomas P J

    2016-02-01

    The elucidation of the molecular mechanisms by which soluble proteins convert into their amyloid forms is a fundamental prerequisite for understanding and controlling disorders that are linked to protein aggregation, such as Alzheimer's and Parkinson's diseases. However, because of the complexity associated with aggregation reaction networks, the analysis of kinetic data of protein aggregation to obtain the underlying mechanisms represents a complex task. Here we describe a framework, using quantitative kinetic assays and global fitting, to determine and to verify a molecular mechanism for aggregation reactions that is compatible with experimental kinetic data. We implement this approach in a web-based software, AmyloFit. Our procedure starts from the results of kinetic experiments that measure the concentration of aggregate mass as a function of time. We illustrate the approach with results from the aggregation of the β-amyloid (Aβ) peptides measured using thioflavin T, but the method is suitable for data from any similar kinetic experiment measuring the accumulation of aggregate mass as a function of time; the input data are in the form of a tab-separated text file. We also outline general experimental strategies and practical considerations for obtaining kinetic data of sufficient quality to draw detailed mechanistic conclusions, and the procedure starts with instructions for extensive data quality control. For the core part of the analysis, we provide an online platform (http://www.amylofit.ch.cam.ac.uk) that enables robust global analysis of kinetic data without the need for extensive programming or detailed mathematical knowledge. The software automates repetitive tasks and guides users through the key steps of kinetic analysis: determination of constraints to be placed on the aggregation mechanism based on the concentration dependence of the aggregation reaction, choosing from several fundamental models describing assembly into linear aggregates and

  3. 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

  4. Chemical decomposition of 5-aza-2'-deoxycytidine (Decitabine): kinetic analyses and identification of products by NMR, HPLC, and mass spectrometry.

    Science.gov (United States)

    Rogstad, Daniel K; Herring, Jason L; Theruvathu, Jacob A; Burdzy, Artur; Perry, Christopher C; Neidigh, Jonathan W; Sowers, Lawrence C

    2009-06-01

    The nucleoside analogue 5-aza-2'-deoxycytidine (Decitabine, DAC) is one of several drugs in clinical use that inhibit DNA methyltransferases, leading to a decrease of 5-methylcytosine in newly replicated DNA and subsequent transcriptional activation of genes silenced by cytosine methylation. In addition to methyltransferase inhibition, DAC has demonstrated toxicity and potential mutagenicity, and can induce a DNA-repair response. The mechanisms accounting for these events are not well understood. DAC is chemically unstable in aqueous solutions, but there is little consensus between previous reports as to its half-life and corresponding products of decomposition at physiological temperature and pH, potentially confounding studies on its mechanism of action and long-term use in humans. Here, we have employed a battery of analytical methods to estimate kinetic rates and to characterize DAC decomposition products under conditions of physiological temperature and pH. Our results indicate that DAC decomposes into a plethora of products, formed by hydrolytic opening and deformylation of the triazine ring, in addition to anomerization and possibly other changes in the sugar ring structure. We also discuss the advantages and problems associated with each analytical method used. The results reported here will facilitate ongoing studies and clinical trials aimed at understanding the mechanisms of action, toxicity, and possible mutagenicity of DAC and related analogues.

  5. Comprehensive chemical kinetic modeling of the oxidation of C8 and larger n-alkanes and 2-methylalkanes

    Energy Technology Data Exchange (ETDEWEB)

    Sarathy, S M; Westbrook, C K; Pitz, W J; Mehl, M; Togbe, C; Dagaut, P; Wang, H; Oehlschlaeger, M; NIemann, U; Seshadri, K; Veloo, P S; Ji, C; Egolfopoulos, F; Lu, T

    2011-03-16

    Conventional petroleum jet and diesel fuels, as well as alternative Fischer-Tropsch (FT) fuels and hydrotreated renewable jet (HRJ) fuels, contain high molecular weight lightly branched alkanes (i.e., methylalkanes) and straight chain alkanes (n-alkanes). Improving the combustion of these fuels in practical applications requires a fundamental understanding of large hydrocarbon combustion chemistry. This research project presents a detailed and reduced chemical kinetic mechanism for singly methylated iso-alkanes (i.e., 2-methylalkanes) ranging from C{sub 8} to C{sub 20}. The mechanism also includes an updated version of our previously published C{sub 8} to C{sub 16} n-alkanes model. The complete detailed mechanism contains approximately 7,200 species 31,400 reactions. The proposed model is validated against new experimental data from a variety of fundamental combustion devices including premixed and nonpremixed flames, perfectly stirred reactors and shock tubes. This new model is used to show how the presence of a methyl branch affects important combustion properties such as laminar flame propagation, ignition, and species formation.

  6. Fuel spray combustion of waste cooking oil and palm oil biodiesel: Direct photography and detailed chemical kinetics

    KAUST Repository

    Kuti, Olawole

    2013-10-14

    This paper studies the ignition processes of two biodiesel from two different feedstock sources, namely waste cooked oil (WCO) and palm oil (PO). They were investigated using the direct photography through high-speed video observations and detailed chemical kinetics. The detailed chemical kinetics modeling was carried out to complement data acquired using the high-speed video observations. For the high-speed video observations, an image intensifier combined with OH* filter connected to a high-speed video camera was used to obtain OH* chemiluminscence image near 313 nm. The OH* images were used to obtain the experimental ignition delay of the biodiesel fuels. For the high-speed video observations, experiments were done at an injection pressure of 100, 200 and 300 MPa using a 0.16 mm injector nozzle. Also a detailed chemical kinetics for the biodiesel fuels was carried out using ac chemical kinetics solver adopting a 0-D reactor model to obtain the chemical ignition delay of the combusting fuels. Equivalence ratios obtained from the experimental ignition delay were used for the detailed chemical kinetics analyses. The Politecnico di Milano\\'s thermochemical and reaction kinetic data were adopted to simulate the ignition processes of the biodiesels using the five fatty acid methyl esters (FAME) major components in the biodiesel fuels. From the high-speed video observations, it was observed that at increasing injection pressure, experimental ignition delay increased as a result of improvement in fuel and air mixing effects. Also the palm oil biodiesel has a shorter ignition delay compared to waste cooked oil biodiesel. This phenomenon could be attributed to the higher cetane number of palm biodiesel. The fuel spray ignition properties depend on both the physical ignition delay and chemical ignition delay. From the detailed chemical kinetic results it was observed that at the low temperature, high ambient pressure conditions reactivity increased as equivalent ratio

  7. The chemical, mechanical, and hydrological evolution of weathering granitoid

    Science.gov (United States)

    Goodfellow, Bradley W.; Hilley, George E.; Webb, Samuel M.; Sklar, Leonard S.; Moon, Seulgi; Olson, Christopher A.

    2016-08-01

    Surprisingly few studies connect the chemical, mechanical, and hydrological evolution of rock as it weathers to saprolite and soil. We assess this coevolution in granodiorite from Monterey Peninsula, California, by measuring changes in bulk chemistry, mineralogy, volumetric strain, the oxidation state of Fe in biotite crystals, tensile strength, abrasion rate, connected porosity, and hydraulic conductivity in samples covering a range of weathering grades. We identify the oxidative dissolution of biotite as the key chemical reaction because of the volumetric expansion that accompanies formation of altered biotite and precipitation of ferrihydrite. We show how the associated accumulation of elastic strain produces an energy density that is sufficient to support rock fracturing over length scales equivalent to constituent crystals. The resulting intragranular and intergranular cracking profoundly reduces tensile strength and increases the abrasion rate, connected porosity, and hydraulic conductivity of the rock matrix. These changes increase the rate of plagioclase weathering, and ultimately the rock disintegrates into grus and clay. Major changes in rock properties can occur with only minor element leaching, and the threshold behavior of weathering that arises from the coevolution of chemical, hydrological, and mechanical properties may be difficult to capture using simplified weathering models that fail to incorporate these properties. Our results, which combine the mechanical and hydrological evolution of weathering rock with more common measurements of chemical changes, should help to more accurately model the effects of, and mechanical and hydrological feedbacks upon, chemical weathering of rock.

  8. A Chemical Kinetics Network for Lightning and Life in Planetary Atmospheres

    Science.gov (United States)

    Rimmer, P. B.; Helling, Ch

    2016-05-01

    There are many open questions about prebiotic chemistry in both planetary and exoplanetary environments. The increasing number of known exoplanets and other ultra-cool, substellar objects has propelled the desire to detect life and prebiotic chemistry outside the solar system. We present an ion-neutral chemical network constructed from scratch, Stand2015, that treats hydrogen, nitrogen, carbon, and oxygen chemistry accurately within a temperature range between 100 and 30,000 K. Formation pathways for glycine and other organic molecules are included. The network is complete up to H6C2N2O3. Stand2015 is successfully tested against atmospheric chemistry models for HD 209458b, Jupiter, and the present-day Earth using a simple one-dimensional photochemistry/diffusion code. Our results for the early Earth agree with those of Kasting for CO2, H2, CO, and O2, but do not agree for water and atomic oxygen. We use the network to simulate an experiment where varied chemical initial conditions are irradiated by UV light. The result from our simulation is that more glycine is produced when more ammonia and methane is present. Very little glycine is produced in the absence of any molecular nitrogen and oxygen. This suggests that the production of glycine is inhibited if a gas is too strongly reducing. Possible applications and limitations of the chemical kinetics network are also discussed.

  9. Chemical kinetics with electrical and gas dynamics modelization for NOx removal in an air corona discharge

    International Nuclear Information System (INIS)

    A non-stationary reactive gas dynamics model in a mono-dimensional geometry, including radial mass diffusion, gas temperature variation and chemical kinetics, is developed in this paper. The aim is to analyse the spatio-temporal evolution of the main neutral species involved in a corona discharge used for NO pollution control in polluted air at atmospheric pressure and ambient temperature. The present reactive gas dynamics model takes into account 16 neutral chemical species (including certain metastable species) reacting following 110 selected chemical reactions. The initial concentration of each neutral species is obtained from a 1.5D electrical discharge model. The gas temperature variations are due to direct Joule heating during the discharge phase, and also result from the delayed heating due to the relaxation of the vibrational energy into a random thermal energy during the post-discharge phase. The simulation conditions are those of an existing experimental setup (anode voltage of 10 kV in the case of a point to plane geometry with an interelectrode distance of 10 mm). The obtained results show that the diffusion phenomena and the gas temperature rise affect quite well the gas reactivity and the neutral species evolution. This allows us to better understand the different reaction processes and transport phenomena affecting the NO concentration magnitude inside the discharge channel. (author)

  10. Leaching Kinetics of Atrazine and Inorganic Chemicals in Tilled and Orchard Soils

    Science.gov (United States)

    Szajdak, Lech W.; Lipiec, Jerzy; Siczek, Anna; Nosalewicz, Artur; Majewska, Urszula

    2014-04-01

    The aim of this study was to verify first-order kinetic reaction rate model performance in predicting of leaching of atrazine and inorganic compounds (K+1, Fe+3, Mg+2, Mn+2, NH4 +, NO3 - and PO4 -3) from tilled and orchard silty loam soils. This model provided an excellent fit to the experimental concentration changes of the compounds vs. time data during leaching. Calculated values of the first-order reaction rate constants for the changes of all chemicals were from 3.8 to 19.0 times higher in orchard than in tilled soil. Higher first-order reaction constants for orchard than tilled soil correspond with both higher total porosity and contribution of biological pores in the former. The first order reaction constants for the leaching of chemical compounds enables prediction of the actual compound concentration and the interactions between compound and soil as affected by management system. The study demonstrates the effectiveness of simultaneous chemical and physical analyses as a tool for the understanding of leaching in variously managed soils.

  11. VULCAN: an Open-Source, Validated Chemical Kinetics Python Code for Exoplanetary Atmospheres

    CERN Document Server

    Tsai, Shang-Min; Grosheintz, Luc; Rimmer, Paul B; Kitzmann, Daniel; Heng, Kevin

    2016-01-01

    We present an open-source and validated chemical kinetics code for studying hot exoplanetary atmospheres, which we name VULCAN. It is constructed for gaseous chemistry from 500 to 2500 K using a reduced C- H-O chemical network with about 300 reactions. It uses eddy diffusion to mimic atmospheric dynamics and excludes photochemistry. We have provided a full description of the rate coefficients and thermodynamic data used. We validate VULCAN by reproducing chemical equilibrium and by comparing its output versus the disequilibrium-chemistry calculations of Moses et al. and Rimmer & Helling. It reproduces the models of HD 189733b and HD 209458b by Moses et al., which employ a network with nearly 1600 reactions. Further validation of VULCAN is made by examining the theoretical trends produced when the temperature-pressure profile and carbon-to-oxygen ratio are varied. Assisted by a sensitivity test designed to identify the key reactions responsible for producing a specific molecule, we revisit the quenching ap...

  12. Two-scale large deviations for chemical reaction kinetics through second quantization path integral

    International Nuclear Information System (INIS)

    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)

  13. Thermodynamic and chemical kinetic analysis of a 5 kw, compact steam reformer - PEMFC system

    Energy Technology Data Exchange (ETDEWEB)

    Acevedo, Luis Evelio Garcia; Oliveira, Amir Antonio Martins [Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil). Dept. de Engenharia Mecanica], e-mail: evelio@labcet.ufsc.br, e-mail: amirol@emc.ufsc.br

    2006-07-01

    Here we present a thermodynamic and chemical kinetic analysis of the methane steam reforming for production of 5 kw of electrical power in a PEM fuel cell. The equilibrium analysis is based on the method of element potentials to find the state of minimum Gibbs free energy for the system and provides the equilibrium concentration of the reforming products. The objective of this analysis is to obtain the range of reforming temperature, pressure and steam-methane molar ratio that results in maximum hydrogen production subjected to low carbon monoxide production and negligible coke formation. The thermal analysis provides the heat transfer rates associated with the individual processes of steam production, gas-phase superheating and reforming necessary to produce 5 kw of electrical power in a PEM fuel cell and allows for the calculation of thermal efficiencies. Then, the chemical reaction pathways for hydrogen production in steam reforming are discussed and the available chemical, adsorption and equilibrium constants are analyzed in terms of thermodynamic consistency. This analysis provides the framework for the reactor sizing and for establishing the adequate operation conditions. (author)

  14. Cholesterol increases kinetic, energetic, and mechanical stability of the human β2-adrenergic receptor

    DEFF Research Database (Denmark)

    Zocher, Michael; Zhang, Cheng; Rasmussen, Søren Gøgsig Faarup;

    2012-01-01

    to quantify the mechanical strength and flexibility, conformational variability, and kinetic and energetic stability of structural segments stabilizing the human β(2)-adrenergic receptor (β(2)AR) in the absence and presence of the cholesterol analog cholesteryl hemisuccinate (CHS). CHS considerably increased...

  15. Mechanism and Kinetics Analysis of NO/SO2/N2/O2 Dissociation Reactions in Non-Thermal Plasma

    Institute of Scientific and Technical Information of China (English)

    WANG Xinliang; LI Tingting; WEI Dongxiang; WEI Yanli; GU Fan

    2008-01-01

    The kinetics mechanism of the dissociation reactions in a NO/SO2/N2/O2 system was investigated in consideration of energetic electrons' impacts on a non-thermal plasma. A model was derived from the Boltzmann equation and molecule collision theory to predict the dissociation reaction rate coefficients. Upon comparison with available literature, the model was confirmed to be acceptably accurate in general. Several reaction rate coefficients of the NO/SO2/N2/O2 dissociation system were derived according to the Arrhenius formula. The activation energies of each plasma reaction were calculated by quantum chemistry methods. The relation between the dissociation reaction rate coefficient and electron temperature was established to describe the importance of each reaction and to predict relevant processes of gaseous chemical reactions. The sensitivity of the mechanism of NO/SO2/N2/O2 dissociation reaction in a non-thermal plasma was also analysed.

  16. miRNA regulatory circuits in ES cells differentiation: a chemical kinetics modeling approach.

    Directory of Open Access Journals (Sweden)

    Zijun Luo

    Full Text Available MicroRNAs (miRNAs play an important role in gene regulation for Embryonic Stem cells (ES cells, where they either down-regulate target mRNA genes by degradation or repress protein expression of these mRNA genes by inhibiting translation. Well known tables TargetScan and miRanda may predict quite long lists of potential miRNAs inhibitors for each mRNA gene, and one of our goals was to strongly narrow down the list of mRNA targets potentially repressed by a known large list of 400 miRNAs. Our paper focuses on algorithmic analysis of ES cells microarray data to reliably detect repressive interactions between miRNAs and mRNAs. We model, by chemical kinetics equations, the interaction architectures implementing the two basic silencing processes of miRNAs, namely "direct degradation" or "translation inhibition" of targeted mRNAs. For each pair (M,G of potentially interacting miRMA gene M and mRNA gene G, we parameterize our associated kinetic equations by optimizing their fit with microarray data. When this fit is high enough, we validate the pair (M,G as a highly probable repressive interaction. This approach leads to the computation of a highly selective and drastically reduced list of repressive pairs (M,G involved in ES cells differentiation.

  17. Kinetically controlled InN nucleation on GaN templates by metalorganic chemical vapour deposition

    International Nuclear Information System (INIS)

    This paper presents a study on the nucleation and initial growth kinetics of InN on GaN, especially their dependence on metalorganic chemical vapour deposition conditions. It is found that the density and size of separated InN nano-scale islands can be adjusted and well controlled by changing the V/III ratio and growth temperature. InN nuclei density increases for several orders of magnitude with decreasing growth temperature between 525 and 375 0C. At lower growth temperatures, InN thin films take the form of small and closely packed islands with diameters less than 100 nm, whereas at elevated temperatures the InN islands grow larger and become well separated, approaching an equilibrium hexagonal shape due to enhanced surface diffusion of adatoms. The temperature dependence of InN island density gives two activation energies of InN nucleation behaviour, which is attributed to two different kinetic processes related to In adatom surface diffusion and desorption, respectively.

  18. The kinetics and mechanism of an aqueous phase isoprene reaction with hydroxyl radical

    OpenAIRE

    Huang, D.; X. Zhang; Chen, Z M; Zhao, Y.; X. L. Shen

    2011-01-01

    Aqueous phase chemical processes of organic compounds in the atmosphere have received increasing attention, partly due to their potential contribution to the formation of secondary organic aerosol (SOA). Here, we analyzed the aqueous OH-initiated oxidation of isoprene and its reaction products including carbonyl compounds and organic acids, regarding the acidity and temperature as in-cloudy conditions. We also performed a laboratory simulation to improve our understanding of the kinetics and ...

  19. Nitric oxide synthesis in the lung. Regulation by oxygen through a kinetic mechanism.

    OpenAIRE

    Dweik, R A; Laskowski, D; Abu-Soud, H M; Kaneko, F; Hutte, R; Stuehr, D J; Erzurum, S. C.

    1998-01-01

    In this study, we show that oxygen regulates nitric oxide (NO) levels through effects on NO synthase (NOS) enzyme kinetics. Initially, NO synthesis in the static lung was measured in bronchiolar gases during an expiratory breath-hold in normal individuals. NO accumulated exponentially to a plateau, indicating balance between NO production and consumption in the lung. Detection of NO2-, NO3-, and S-nitrosothiols in lung epithelial lining fluids confirmed NO consumption by chemical reactions in...

  20. Time-resolved broadband cavity-enhanced absorption spectroscopy for chemical kinetics.

    Energy Technology Data Exchange (ETDEWEB)

    Sheps, Leonid; Chandler, David W.

    2013-04-01

    Experimental measurements of elementary reaction rate coefficients and product branching ratios are essential to our understanding of many fundamentally important processes in Combustion Chemistry. However, such measurements are often impossible because of a lack of adequate detection techniques. Some of the largest gaps in our knowledge concern some of the most important radical species, because their short lifetimes and low steady-state concentrations make them particularly difficult to detect. To address this challenge, we propose a novel general detection method for gas-phase chemical kinetics: time-resolved broadband cavity-enhanced absorption spectroscopy (TR-BB-CEAS). This all-optical, non-intrusive, multiplexed method enables sensitive direct probing of transient reaction intermediates in a simple, inexpensive, and robust experimental package.

  1. Weak Dynamic Non-Emptiability and Persistence of Chemical Kinetics Systems

    CERN Document Server

    Johnston, Matthew D

    2010-01-01

    A frequently desirable characteristic of chemical kinetics systems is that of persistence, the property that no initially present species may tend toward extinction. It is known that solutions of deterministically modelled mass-action systems may only approach portions of the boundary of the positive orthant which correspond to semi-locking sets (alternatively called siphons). Consequently, most recent work on persistence of these systems has been focused on these sets. In this paper, we focus on a result which states that, for a conservative mass-action system, persistence holds if every critical semi-locking set is dynamically non-emptiable and the system contains no nested locking sets. We will generalize this result by introducing the notion of a weakly dynamically non-emptiable semi-locking set and making novel use of the well-known Farkas' Lemma. We will also connect this result to known results regarding complex balanced systems and systems with facets.

  2. Infrared Absorption Spectroscopy and Chemical Kinetics of Free Radicals, Final Technical Report

    Science.gov (United States)

    Curl, Robert F.; Glass, Graham P.

    2004-11-01

    This research was directed at the detection, monitoring, and study of the chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. Work on the reaction of OH with acetaldehyde has been completed and published and work on the reaction of O({sup 1}D) with CH{sub 4} has been completed and submitted for publication. In the course of our investigation of branching ratios of the reactions of O({sup 1}D) with acetaldehyde and methane, we discovered that hot atom chemistry effects are not negligible at the gas pressures (13 Torr) initially used. Branching ratios of the reaction of O({sup 1}D) with CH{sub 4} have been measured at a tenfold higher He flow and fivefold higher pressure.

  3. Optimization of chemical reactor feed by simulations based on a kinetic approach.

    Science.gov (United States)

    Guinand, Charles; Dabros, Michal; Roduit, Bertrand; Meyer, Thierry; Stoessel, Francis

    2014-10-01

    Chemical incidents are typically caused by loss of control, resulting in runaway reactions or process deviations in different stages of the production. In the case of fed-batch reactors, the problem generally encountered is the accumulation of heat. This is directly related to the temperature of the process, the reaction kinetics and adiabatic temperature rise, which is the maximum temperature attainable in the event of cooling failure. The main possibility to control the heat accumulation is the use of a well-controlled adapted feed. The feed rate can be adjusted by using reaction and reactor dynamic models coupled to Model Predictive Control. Thereby, it is possible to predict the best feed profile respecting the safety constraints.

  4. Coherent chemical kinetics as quantum walks. I. Reaction operators for radical pairs

    Science.gov (United States)

    Chia, A.; Tan, K. C.; Pawela, Ł.; Kurzyński, P.; Paterek, T.; Kaszlikowski, D.

    2016-03-01

    Classical chemical kinetics uses rate-equation models to describe how a reaction proceeds in time. Such models are sufficient for describing state transitions in a reaction where coherences between different states do not arise, in other words, a reaction that contains only incoherent transitions. A prominent example of a reaction containing coherent transitions is the radical-pair model. The kinetics of such reactions is defined by the so-called reaction operator that determines the radical-pair state as a function of intermediate transition rates. We argue that the well-known concept of quantum walks from quantum information theory is a natural and apt framework for describing multisite chemical reactions. By composing Kraus maps that act only on two sites at a time, we show how the quantum-walk formalism can be applied to derive a reaction operator for the standard avian radical-pair reaction. Our reaction operator predicts the same recombination dephasing rate as the conventional Haberkorn model, which is consistent with recent experiments [K. Maeda et al., J. Chem. Phys. 139, 234309 (2013), 10.1063/1.4844355], in contrast to previous work by Jones and Hore [J. A. Jones and P. J. Hore, Chem. Phys. Lett. 488, 90 (2010), 10.1016/j.cplett.2010.01.063]. The standard radical-pair reaction has conventionally been described by either a normalized density operator incorporating both the radical pair and reaction products or a trace-decreasing density operator that considers only the radical pair. We demonstrate a density operator that is both normalized and refers only to radical-pair states. Generalizations to include additional dephasing processes and an arbitrary number of sites are also discussed.

  5. Characterization of Chemical and Mechanical Properties of Polymer Based Nanocomposites

    OpenAIRE

    Wafy, Tamer

    2013-01-01

    Characterization of Chemical and Mechanical Properties of Polymer Based NanocompositesThe University of ManchesterTamer Wafy Doctor of Philosophy17 January, 2013One of the most significant issues in nanocomposite performance is improving the dispersion of carbon nanotubes (CNTs) in thermosetting or thermoplastic polymers in order to gain good mechanical properties. Several studies have investigated the fabrication of nanocomposites based on carbon nanotubes and analysed properties, but there ...

  6. Investigation of Spark Ignition and Autoignition in Methane and Air Using Computational Fluid Dynamics and Chemical Reaction Kinetics. A numerical Study of Ignition Processes in Internal Combustion Engines

    Energy Technology Data Exchange (ETDEWEB)

    Nordrik, R.

    1993-12-01

    The processes in the combustion chamber of internal combustion engines have received increased attention in recent years because their efficiencies are important both economically and environmentally. This doctoral thesis studies the ignition phenomena by means of numerical simulation methods. The fundamental physical relations include flow field conservation equations, thermodynamics, chemical reaction kinetics, transport properties and spark modelling. Special attention is given to the inclusion of chemical kinetics in the flow field equations. Using his No Transport of Radicals Concept method, the author reduces the computational efforts by neglecting the transport of selected intermediate species. The method is validated by comparison with flame propagation data. A computational method is described and used to simulate spark ignition in laminar premixed methane-air mixtures and the autoignition process of a methane bubble surrounded by hot air. The spark ignition simulation agrees well with experimental results from the literature. The autoignition simulation identifies the importance of diffusive and chemical processes acting together. The ignition delay times exceed the experimental values found in the literature for premixed ignition delay, presumably because of the mixing process and lack of information on low temperature reactions in the skeletal kinetic mechanism. Transient turbulent methane jet autoignition is simulated by means of the KIVA-II code. Turbulent combustion is modelled by the Eddy Dissipation Concept. 90 refs., 81 figs., 3 tabs.

  7. Kinetic mechanism of vanillyl-alcohol oxidase with short-chain 4-alkylphenols

    OpenAIRE

    Fraaije, Marco W.; Heuvel, Robert H.H. van den; Roelofs, Jules C.A.A.; van Berkel, Willem J H

    1998-01-01

    The kinetic mechanism of vanillyl-alcohol oxidase with 4-methylphenol, 4-ethylphenol, 4-propylphenol and their Cα-deuterated analogs has been studied at pH 7.5 and 25°C. Conversion of 4-methylphenol is extremely slow (0.005 s-1) while the enzyme is largely in the reduced form during turnover. 4-Ethylphenol and 4-propylphenol are readily converted while the enzyme is mainly in the oxidized form during turnover. The deuterium kinetic isotope effect for overall catalysis ranges between 7-10 wher...

  8. ′ Precipitation and Growth Kinetics in Mechanically Alloyed Ni–Al

    OpenAIRE

    Tang, Qingxin; Ukai, Shigeharu; Minami, Akinobu; Hayashi, Shigenari

    2011-01-01

    The precipitation and growth kinetics of γ′ precipitates, which are strengthening factors in Ni-base oxide dispersion strengthened (ODS) superalloys, were investigated. The cuboidal-type γ′ precipitates are formed in conventional arc-melted Ni–Al alloys, whereas spherical-type precipitates are formed in the mechanically alloyed (MAed) specimens. The morphology is controlled by a lattice misfit between the γ′ precipitates and the matrix at the aging temperature of 800°C. The growth kinetics of...

  9. Afterglow kinetics and storage mechanism in CaF{sub 2}:Mn (TLD-400)

    Energy Technology Data Exchange (ETDEWEB)

    Danilkin, M. [Faculty of Physics and Chemistry, University of Tartu, Taehe 4, 51010 Tartu (Estonia)], E-mail: danilkin@ut.ee; Lust, A.; Ratas, A.; Seeman, V.; Kerikmaee, M. [Faculty of Physics and Chemistry, University of Tartu, Taehe 4, 51010 Tartu (Estonia)

    2008-02-15

    Thermoluminescence (TL) of CaF{sub 2}:Mn and the isothermal afterglow curves were studied after a pre-annealing of irradiated samples. Afterglow kinetics can be easily approximated with two exponents. A simple kinetic model is suggested. The TL main peak activation energy (1.597 eV) is very close to the dissociation energy of F{sub 2} molecule (1.606 eV) and exceeds the thermal decay activation energies of all the other intrinsic defects previously known in CaF{sub 2}. A mechanism of energy storage and release is discussed.

  10. Self-organized evolution of mechanism kinetic scheme based on axiomatic design

    Institute of Scientific and Technical Information of China (English)

    Feng Yixiong; Tan Jianrong; Wei Zhe; Hao He

    2007-01-01

    The self-organized evolution technology of the mechanism kinetic scheme based on axiomatic design is presented.This technology tries to express the constraints between kinetic mechanisms briefly in a semantic form which is more familiar to the designers.Though the mapping process between the kinetic chain unit and the unit instance,the evolution from abstract unit to concrete engineering instance is achieved.The subdivision of unit coupling semantics is studied.and the evolution of semantics is finished.Also.the semantic constraints evolution of unit coupling semantics is described.The product structure models with function and assembly meanings are constructed based on the kinematic chain unit and unit coupling.It provides a basis to realize the inheritance and transfer of constraint information from conceptual design to design for assembly(DFA).As the engineering practice result shows,the method Can help the engineers express their design intension more clearly and naturally in a high semantic level.And the automation,recursion and visualization of the mechanism kinetic scheme design are realized.

  11. LSENS: A General Chemical Kinetics and Sensitivity Analysis Code for homogeneous gas-phase reactions. Part 3: Illustrative test problems

    Science.gov (United States)

    Bittker, David A.; Radhakrishnan, Krishnan

    1994-01-01

    LSENS, the Lewis General Chemical Kinetics and Sensitivity Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part 3 of a series of three reference publications that describe LSENS, provide a detailed guide to its usage, and present many example problems. Part 3 explains the kinetics and kinetics-plus-sensitivity analysis problems supplied with LSENS and presents sample results. These problems illustrate the various capabilities of, and reaction models that can be solved by, the code and may provide a convenient starting point for the user to construct the problem data file required to execute LSENS. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions.

  12. Quantum chemical investigation of mechanisms of silane oxidation

    DEFF Research Database (Denmark)

    Mader, Mary M.; Norrby, Per-Ola

    2001-01-01

    Several mechanisms for the peroxide oxidation of organosilanes to alcohols are compared by quantum chemical calculations, including solvation with the PCM method. Without doubt, the reaction proceeds via anionic, pentacoordinate silicate species, but a profound difference is found between in vacuo...

  13. Kinetics and mechanism of the oxidation of some diols by benzyltrimethylammonium tribromide

    Indian Academy of Sciences (India)

    Garima Goswami; Seema Kothari; Kalyan K Banerji

    2001-02-01

    The kinetics of oxidation of five vicinal and four non-vicinal diols, and two of their monoethers by benzyltrimethylammonium tribromide (BTMAB) have been studied in 3:7 (/) acetic acid-water mixture. The vicinal diols yield the carbonyl compounds arising out of the glycol bond fission while the other diols give the hydroxycarbonyl compounds. The reaction is first-order with respect to BTMAB. Michaelis-Menten type kinetics is observed with respect to diol. Addition of benzyltrimethylammonium chloride does not affect the rate. Tribromide ion is postulated to be the reactive oxidizing species. Oxidation of [1,1,2,2-2H4] ethanediol shows the absence of a kinetic isotope effect. The reaction exhibits substantial solvent isotope effect. A mechanism involving a glycol-bond fission has been proposed for the oxidation of the vicinal diols. The other diols are oxidized by a hydride ion transfer to the oxidant, as are the monohydric alcohols.

  14. Kinetic Analysis of the Anodic Carbon Oxidation Mechanism in a Molten Carbonate Medium

    International Nuclear Information System (INIS)

    The oxidation mechanism for carbon in a carbonate melt was modelled using an electrochemical kinetic approach. Through the Butler-Volmer equation for electrode kinetics, a series of expressions was derived assuming each step of the proposed carbon oxidation mechanism is in turn the rate determining step (RDS). Through the derived expressions the transfer coefficient and Tafel slope were calculated for each possible RDS of the proposed mechanism and these were compared with real data collected on carbon based electrodes including graphite and coal. It was established that the RDS of the electrochemical oxidation process is dependent on both the carbon type and the potential region of oxidation. The simplified kinetic analysis suggested that the RDS in the main oxidation region is likely to be the first or second electron transfer on a graphite electrode surface, which occurs following initial adsorption of an oxygen anion to an active carbon site. This is contrary to previous suggestions that adsorption of the second anion to the carbon surface will be rate determining. It was further shown that use of a coal based carbon introduces a change in mechanism with an additional reaction region where a different mechanism is proposed to be operating

  15. Mechanism and kinetics study on the OH-initiated oxidation of organophosphorus pesticide trichlorfon in atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Bao, Yuan; Zhang, Chenxi; Yang, Wenbo; Hu, Jingtian [Environment Research Institute, Shandong University, Jinan 250100 (China); Sun, Xiaomin, E-mail: sxmwch@sdu.edu.cn [Environment Research Institute, Shandong University, Jinan 250100 (China); State Key Laboratory of Solid Lubrication, Lanzhou Institute of Chemical Physics, Chinese Academy Of Science, Lanzhou 730000 (China)

    2012-03-01

    Trichlorfon [O,O-dimethyl-(2,2,2-trichloro-1-hydroxy-ethyl) phosphonate] (TCF) is a kind of widely used organophosphorus pesticides. In this paper, the mechanism and possible oxidation products for the OH-initiated reactions of TCF are studied at the MPWB1K/6-311 + G(3df,2p)//MPWB1K/6-31 + G(d,p) level. The study shows that H abstraction reaction from the CH{sub 3} group and the CH group as well as OH addition reaction to the P atom are energetically favorable for the reactions of TCF and the main products are (CH{sub 3}O){sub 2}POOH (P1), CCl{sub 3}CHOHPOOH(OCH{sub 3}) (P2), CH{sub 3}OPO{sub 2} (P3), CCl{sub 3}COPO(OCH{sub 3}){sub 2} (P6) and HCHO. On the basis of the quantum chemical information, the kinetic calculation is performed and the rate constants are calculated over a temperature range of 200-800 K using the transition state theory and canonical variational transition state theory with small-curvature tunneling effect. The Arrhenius formulas of rate constants with the temperature are fitted and the lifetimes of the reaction species in the troposphere are estimated according to the rate constants, which can provide helpful information for the model simulation study. - Highlights: Black-Right-Pointing-Pointer The H-abstracted reaction and OH addition reaction are favorable channels. Black-Right-Pointing-Pointer The Arrhenius formulas of rate constants with the temperature are fitted. Black-Right-Pointing-Pointer The rate constants of TCF relative to OH radical is 4.95 Multiplication-Sign 10{sup -15} cm{sup 3} molecule{sup -1} s{sup -1}.

  16. Animal manure phosphorus characterization by sequential chemical fractionation, release kinetics and 31P-NMR analysis

    Directory of Open Access Journals (Sweden)

    Tales Tiecher

    2014-10-01

    Full Text Available Phosphate release kinetics from manures are of global interest because sustainable plant nutrition with phosphate will be a major concern in the future. Although information on the bioavailability and chemical composition of P present in manure used as fertilizer are important to understand its dynamics in the soil, such studies are still scarce. Therefore, P extraction was evaluated in this study by sequential chemical fractionation, desorption with anion-cation exchange resin and 31P nuclear magnetic resonance (31P-NMR spectroscopy to assess the P forms in three different dry manure types (i.e. poultry, cattle and swine manure. All three methods showed that the P forms in poultry, cattle and swine dry manures are mostly inorganic and highly bioavailable. The estimated P pools showed that organic and recalcitrant P forms were negligible and highly dependent on the Ca:P ratio in manures. The results obtained here showed that the extraction of P with these three different methods allows a better understanding and complete characterization of the P pools present in the manures.

  17. Semi-gas kinetics model for performance modeling of flowing chemical oxygen-iodine lasers (COIL)

    Institute of Scientific and Technical Information of China (English)

    GAO Zhi; HU Limin; SHEN Yiqing

    2004-01-01

    A semi-gas kinetics (SGK) model for performance analyses of flowing chemical oxygen-iodine laser (COIL) is presented. In this model, the oxygen-iodine reaction gas flow is treated as a continuous medium, and the effect of thermal motions of particles of different laser energy levels on the performances of the COIL is included and the velocity distribution function equations are solved by using the double-parameter perturbational method. For a premixed flow, effects of different chemical reaction systems, different gain saturation models and temperature, pressure, yield of excited oxygen, iodine concentration and frequency-shift on the performances of the COIL are computed, and the calculated output power agrees well with the experimental data. The results indicate that the power extraction of the SGK model considering 21 reactions is close to those when only the reversible pumping reaction is considered, while different gain saturation models and adjustable parameters greatly affect the output power, the optimal threshold gain range, and the length of power extraction.

  18. On inelastic reactive collisions in kinetic theory of chemically reacting gas mixtures

    Science.gov (United States)

    Kremer, Gilberto M.; Silva, Adriano W.; Alves, Giselle M.

    2010-07-01

    A kinetic theory for a simple reversible reaction-characterized by a binary mixture of ideal gases whose constituents denoted by A and B undergo a reaction of the type A+A⇌B+B-is developed by considering the reactive collisions as inelastic ones. The geometry of the collision is taken into account in the line-of-centers differential cross section by allowing that a chemical reaction may occur only when the energy of the relative velocity in the direction of the line which joins the centers of the molecules at collision is larger than the activation energy. It is shown that the restitution coefficients: (i) depend explicitly on the reaction heat and on the relative translational energy in the direction of the line which joins the centers of the molecules during an inelastic collision; (ii) vanish when the reaction heat is zero; (iii) are larger or smaller than one depending on the direction of the reaction and on the sign of the reaction heat. First approximations to the distribution functions are determined from the system of Boltzmann equations for the last stage of a chemical reaction. It is shown that the deviations from the Maxwellian distribution functions and the production terms of the particle number densities: (i) vanish when the reaction heat is zero provided that the affinity is close to zero and (ii) are negative or positive depending on the sign of the reaction heat and on the direction of the reaction.

  19. Composting kinetics in full-scale mechanical-biological treatment plants.

    Science.gov (United States)

    Baptista, Marco; Antunes, Fernando; Gonçalves, Manuel Souteiro; Morvan, Bernard; Silveira, Ana

    2010-10-01

    This study focuses on the investigation of the kinetics of municipal solid waste composting in three full-scale mechanical-biological treatment (MBT) plants. The aims were to test a kinetic model based on volatile solids (VS) content change for describing the composting process in MBT plants, and to identify the model parameters that affected the estimation of the reaction rate constant most. To achieve this, VS content and several environmental conditions, namely temperature, moisture content, oxygen concentration and total bulk density were monitored throughout the composting process. Experimental data was fitted with a first-order kinetic model, and a rate constant (k) characteristic of composting under optimum environmental conditions was obtained. The kinetic model satisfactorily described the experimental data for the three MBT plants. k values ranged from 0.043+/-0.002 d(-1) to 0.082+/-0.011 d(-1). Sensitivity analysis showed that the model parameters that most affected the estimation of k were the initial biodegradable volatile solids content, the maximum temperature for biodegradation and the optimum moisture content. In conclusion, we show for the first time that full-scale MBT plants can be successfully modelled with a composting kinetic model. PMID:20493677

  20. Devitrification kinetics and phase selection mechanisms in Cu-Zr metallic glasses

    Energy Technology Data Exchange (ETDEWEB)

    Kalay, Ilkay [Iowa State Univ., Ames, IA (United States)

    2010-01-01

    research on the behaviors of glass forming alloys. Further motivation arising from the application of this system as a basis for many BMGs and ACC materials; the Cu-Zr system warrants this attention and offers great potential for the development of new materials. However, the prediction and control of microstructural evolution during devitrification remains challenging because of the complex devitrification behavior of the Cu-Zr binary alloy which is arising from the competition of metastable and stable phases and diversity of crystal structures. This dissertation details a systematic fundamental investigation into the mechanisms and kinetics of the various crystallization transformation processes involved in the overall devitrification response of Cu-Zr and Cu-Zr-Al glasses. Various isothermal and nonisothermal treatments are employed, and the structural response is characterized using bulk X-ray and thermal analysis methods as well as nanoscale microscopic analysis methods, revealing structural and chemical details down to the atomic-scale. By carefully combining techniques such as differential scanning calorimetry (DSC), in-situ synchrotron high energy X-ray diffraction (HEXRD), and transmission electron microscopy (TEM) to quantify the characterization transformations, this research has uncovered numerous details concerning the atomistic mechanisms of crystallization and has provided much new understanding related to the dominant phases, the overall reaction sequences, and the rate-controlling mechanisms. As such this work represents a substantial step forward in understanding these transformations and provides a clear framework for further progress toward ultimate application of controlled devitrification processing for the production of new materials with remarkable properties.

  1. Sensitivity of Polar Stratospheric Ozone Loss to Uncertainties in Chemical Reaction Kinetics

    Science.gov (United States)

    Kawa, S. Randolph; Stolarksi, Richard S.; Douglass, Anne R.; Newman, Paul A.

    2008-01-01

    Several recent observational and laboratory studies of processes involved in polar stratospheric ozone loss have prompted a reexamination of aspects of our understanding for this key indicator of global change. To a large extent, our confidence in understanding and projecting changes in polar and global ozone is based on our ability to simulate these processes in numerical models of chemistry and transport. The fidelity of the models is assessed in comparison with a wide range of observations. These models depend on laboratory-measured kinetic reaction rates and photolysis cross sections to simulate molecular interactions. A typical stratospheric chemistry mechanism has on the order of 50- 100 species undergoing over a hundred intermolecular reactions and several tens of photolysis reactions. The rates of all of these reactions are subject to uncertainty, some substantial. Given the complexity of the models, however, it is difficult to quantify uncertainties in many aspects of system. In this study we use a simple box-model scenario for Antarctic ozone to estimate the uncertainty in loss attributable to known reaction kinetic uncertainties. Following the method of earlier work, rates and uncertainties from the latest laboratory evaluations are applied in random combinations. We determine the key reactions and rates contributing the largest potential errors and compare the results to observations to evaluate which combinations are consistent with atmospheric data. Implications for our theoretical and practical understanding of polar ozone loss will be assessed.

  2. An insight into chemical kinetics and turbulence-chemistry interaction modeling in flameless combustion

    OpenAIRE

    Amir Azimi, Javad Aminian

    2015-01-01

    Computational Fluid Dynamics (CFD) study of flameless combustion condition is carried out by solving the Reynolds-Averaged Navier-Stokes (RANS) equations in the open-source CFD package of OpenFOAM 2.1.0. Particular attention is devoted to the comparison of three global and detailed chemical mechanisms using the Partially Stirred Reactor (PaSR) combustion model for the turbulence-chemistry interaction treatment. The OpenFOAM simulations are assessed against previously published CFD results usi...

  3. Fourier-Domain Analysis of Hydriding Kinetics Using Pneumato-Chemical Impedance Spectroscopy

    OpenAIRE

    Millet, P.; C. Decaux; R. Ngameni; Guymont, M.

    2007-01-01

    Analysis of phase transformation processes observed in hydrogen absorbing materials (pure metals, alloys, or compounds) is still a matter of active research. Using pneumato-chemical impedance spectroscopy (PIS), it is now possible to analyze the mechanism of hydriding reactions induced by the gas phase. Experimental impedance diagrams, measured on activated LaNi5 in single- and two-phase domains, are reported in this paper. It is shown that their shape is mostly affected by the slope of the i...

  4. Mechanism and kinetics of the oxidation of synthetic alpha-NiS

    Directory of Open Access Journals (Sweden)

    BOYAN BOYANOV

    2008-02-01

    Full Text Available The results of an investigation of the mechanism and kinetics of the oxidation process of synthetic a-NiS are presented in this paper. The mechanism of a-NiS oxidation was investigated based on the comparative analysis of DTA–TG–DTG and XRD results, as well as the constructed phase stability diagrams (PSD for the Ni–S–O system. The kinetic investigations of the oxidation process were performed under isothermal conditions (temperature range 823–1073 K. The obtained degrees of desulfurization were used in the calculation process according to the Sharp model and the kinetic parameters, including the activation energies and the rate constants of the characteristic reactions, for the oxidation of a-NiS were determined. These results enabled the formulation of a kinetic equation for the desulfurization process: ‑ln(1−a = k1t = 27.89 exp(–9860/Tt, with an activation energy of 82±4 kJ mol-1, for the first stage of the process and –ln (1 − a = k2t = 1.177 exp(–4810/Tt, with an activation energy of 40±2 kJ mol-1, for the second stage.

  5. Modulation of mechanical resonance by chemical potential oscillation in graphene

    Science.gov (United States)

    Chen, Changyao; Deshpande, Vikram V.; Koshino, Mikito; Lee, Sunwoo; Gondarenko, Alexander; MacDonald, Allan H.; Kim, Philip; Hone, James

    2016-03-01

    The classical picture of the force on a capacitor assumes a large density of electronic states, such that the electrochemical potential of charges added to the capacitor is given by the external electrostatic potential and the capacitance is determined purely by geometry. Here we consider capacitively driven motion of a nano-mechanical resonator with a low density of states, in which these assumptions can break down. We find three leading-order corrections to the classical picture: the first of which is a modulation in the static force due to variation in the internal chemical potential; the second and third are changes in the static force and dynamic spring constant due to the rate of change of chemical potential, expressed as the quantum (density of states) capacitance. As a demonstration, we study capacitively driven graphene mechanical resonators, where the chemical potential is modulated independently of the gate voltage using an applied magnetic field to manipulate the energy of electrons residing in discrete Landau levels. In these devices, we observe large periodic frequency shifts consistent with the three corrections to the classical picture. In devices with extremely low strain and disorder, the first correction term dominates and the resonant frequency closely follows the chemical potential. The theoretical model fits the data with only one adjustable parameter representing disorder-broadening of the Landau levels. The underlying electromechanical coupling mechanism is not limited by the particular choice of material, geometry, or mechanism for variation in the chemical potential, and can thus be extended to other low-dimensional systems.

  6. Sorption kinetics and microbial biodegradation activity of hydrophobic chemicals in sewage sludge: Model and measurements based on free concentrations

    NARCIS (Netherlands)

    Artola-Garicano, E.; Borkent, I.; Damen, K.; Jager, T.; Vaes, W.H.J.

    2003-01-01

    In the current study, a new method is introduced with which the rate-limiting factor of biodegradation processes of hydrophobic chemicals in organic and aqueous systems can be determined. The novelty of this approach lies in the combination of a free concentration-based kinetic model with measuremen

  7. 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…

  8. Is Case-Based Learning an Effective Teaching Strategy to Challenge Students' Alternative Conceptions regarding Chemical Kinetics?

    Science.gov (United States)

    Yalcinkaya, Eylem; Tastan-Kirik, Ozgecan; Boz, Yezdan; Yildiran, Demet

    2012-01-01

    Background: Case-based learning (CBL) is simply teaching the concept to the students based on the cases. CBL involves a case, which is a scenario based on daily life, and study questions related to the case, which allows students to discuss their ideas. Chemical kinetics is one of the most difficult concepts for students in chemistry. Students…

  9. Chemical kinetics in the gas phase pulse radiolysis of hydrogen sulfide systems

    International Nuclear Information System (INIS)

    Formations and decays of HS and HS2 radicals in the gas phase pulse radiolysis of pure H2S, H2S/Ar and H2S/H2 systems have been followed directly by kinetic spectroscopy. The literature on the subject is reviewed and a complete reaction scheme is discussed. Computer simulations have been used to check the validity of the proposed mechanisms. Rate constants ksub(HS+HS) = (2.0+-0.4) x 1010 M-1s-1 and ksub(H+H2S) = (6.0+-1.2)x 108 M-1s-1 have been determined. The reaction of HS radicals with S atoms is responsible for the HS2 formation. Pseudo-first order rate constants for reactions of HS with 1.3 butadiene, ethylene and molecular oxygen are reported. (author)

  10. The kinetics and mechanism of an aqueous phase isoprene reaction with hydroxyl radical

    Directory of Open Access Journals (Sweden)

    D. Huang

    2011-08-01

    Full Text Available Aqueous phase chemical processes of organic compounds in the atmosphere have received increasing attention, partly due to their potential contribution to the formation of secondary organic aerosol (SOA. Here, we analyzed the aqueous OH-initiated oxidation of isoprene and its reaction products including carbonyl compounds and organic acids, regarding the acidity and temperature as in-cloudy conditions. We also performed a laboratory simulation to improve our understanding of the kinetics and mechanisms for the products of aqueous isoprene oxidation that are significant precursors of SOA; these included methacrolein (MACR, methyl vinyl ketone (MVK, methyl glyoxal (MG, and glyoxal (GL. We used a novel chemical titration method to monitor the concentration of isoprene in the aqueous phase. We used a box model to interpret the mechanistic differences between aqueous and gas phase OH radical-initiated isoprene oxidations. Our results were the first demonstration of the rate constant for the reaction between isoprene and OH radical in water, 1.2 ± 0.4 × 1010 M−1 s−1 at 283 K. Molar yields were determined based on consumed isoprene. Of note, the ratio of the yields of MVK (24.1 ± 0.8 % to MACR (10.9 ± 1.1% in the aqueous phase isoprene oxidation was approximately double that observed for the corresponding gas phase reaction. We hypothesized that this might be explained by a water-induced enhancement in the self-reaction of a hydroxy isoprene peroxyl radical (HOCH2C(CH3(O2CH = CH2 produced in the aqueous reaction. The observed yields for MG and GL were 11.4 ± 0.3 % and 3.8 ± 0.1 %, respectively. Model simulations indicated that several potential pathways may contribute to the formation of MG and GL. Finally, oxalic acid increased steadily throughout the course of the study, even after isoprene was consumed completely. The observed yield of oxalic acid was 26.2 ± 0

  11. Coupled Thermal-Chemical-Mechanical Modeling of Validation Cookoff Experiments

    Energy Technology Data Exchange (ETDEWEB)

    ERIKSON,WILLIAM W.; SCHMITT,ROBERT G.; ATWOOD,A.I.; CURRAN,P.D.

    2000-11-27

    The cookoff of energetic materials involves the combined effects of several physical and chemical processes. These processes include heat transfer, chemical decomposition, and mechanical response. The interaction and coupling between these processes influence both the time-to-event and the violence of reaction. The prediction of the behavior of explosives during cookoff, particularly with respect to reaction violence, is a challenging task. To this end, a joint DoD/DOE program has been initiated to develop models for cookoff, and to perform experiments to validate those models. In this paper, a series of cookoff analyses are presented and compared with data from a number of experiments for the aluminized, RDX-based, Navy explosive PBXN-109. The traditional thermal-chemical analysis is used to calculate time-to-event and characterize the heat transfer and boundary conditions. A reaction mechanism based on Tarver and McGuire's work on RDX{sup 2} was adjusted to match the spherical one-dimensional time-to-explosion data. The predicted time-to-event using this reaction mechanism compares favorably with the validation tests. Coupled thermal-chemical-mechanical analysis is used to calculate the mechanical response of the confinement and the energetic material state prior to ignition. The predicted state of the material includes the temperature, stress-field, porosity, and extent of reaction. There is little experimental data for comparison to these calculations. The hoop strain in the confining steel tube gives an estimation of the radial stress in the explosive. The inferred pressure from the measured hoop strain and calculated radial stress agree qualitatively. However, validation of the mechanical response model and the chemical reaction mechanism requires more data. A post-ignition burn dynamics model was applied to calculate the confinement dynamics. The burn dynamics calculations suffer from a lack of characterization of the confinement for the flaw

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

    International Nuclear Information System (INIS)

    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

  13. A Visual Demonstration of Solvent Effect in Chemical Kinetics through Blue Bottle Experiment

    Directory of Open Access Journals (Sweden)

    *R. Azmat

    2013-03-01

    Full Text Available In the study of chemical kinetics, usually solvent effect was explained to show the consequences on rate of reaction theoretically which is difficult to understand for under graduate students. The blue bottle experiment as a “one day activity” can be used to explain well visually the solvent effect through demonstration of color change. Kinetics of reduction of methylene green by sucrose and mannose in pure and aqueous methanol medium in presence of NaOH has been investigated for demonstration of solvent effect. The two sugars sucrose and mannose were selected for the experiment those acts as a reducing agents in a basic solution and reduces the methylene green into colorless form. The progress of this reduction reaction was followed by the color changes that the methylene green goes through in variable percentage of alcohol. When the bottle is shaken the oxygen in the air mixes with the solution and oxidizes the methylene green back to its intermediate state (purple. The color of the solution will gradually change and become purple (intermediate and then colorless in 5-10% methanol but in pure methanol color transition were Blue-> purple-> pink indicate the color due to the alcoholic medium. It was observed that increase in percentage in the solvent composition decrease the rate of reduction. The pink color continues due to alcoholic medium which may be attributed with the solvent effect. The observed variation in reading with solvent compositions has been interpreted in terms of interactions of media with the reacting species and the transitions state involved in this reaction.

  14. Sensitivity of polar stratospheric ozone loss to uncertainties in chemical reaction kinetics

    Directory of Open Access Journals (Sweden)

    S. R. Kawa

    2009-06-01

    Full Text Available The impact and significance of uncertainties in model calculations of stratospheric ozone loss resulting from known uncertainty in chemical kinetics parameters is evaluated in trajectory chemistry simulations for the Antarctic and Arctic polar vortices. The uncertainty in modeled ozone loss is derived from Monte Carlo scenario simulations varying the kinetic (reaction and photolysis rate parameters within their estimated uncertainty bounds. Simulations of a typical winter/spring Antarctic vortex scenario and Match scenarios in the Arctic produce large uncertainty in ozone loss rates and integrated seasonal loss. The simulations clearly indicate that the dominant source of model uncertainty in polar ozone loss is uncertainty in the Cl2O2 photolysis reaction, which arises from uncertainty in laboratory-measured molecular cross sections at atmospherically important wavelengths. This estimated uncertainty in JCl2O2 from laboratory measurements seriously hinders our ability to model polar ozone loss within useful quantitative error limits. Atmospheric observations, however, suggest that the Cl2O2 photolysis uncertainty may be less than that derived from the lab data. Comparisons to Match, South Pole ozonesonde, and Aura Microwave Limb Sounder (MLS data all show that the nominal recommended rate simulations agree with data within uncertainties when the Cl2O2 photolysis error is reduced by a factor of two, in line with previous in situ ClOx measurements. Comparisons to simulations using recent cross sections from Pope et al. (2007 are outside the constrained error bounds in each case. Other reactions producing significant sensitivity in polar ozone loss include BrO+ClO and its branching ratios. These uncertainties challenge our confidence in modeling polar ozone depletion and projecting future changes in response to changing halogen

  15. Dominant particles and reactions in a two-temperature chemical kinetic model of a decaying SF6 arc

    Science.gov (United States)

    Wang, Xiaohua; Gao, Qingqing; Fu, Yuwei; Yang, Aijun; Rong, Mingzhe; Wu, Yi; Niu, Chunping; Murphy, Anthony B.

    2016-03-01

    This paper is devoted to the computation of the non-equilibrium composition of an SF6 plasma, and determination of the dominant particles and reactions, at conditions relevant to high-voltage circuit breakers after current zero (temperatures from 12 000 K to 1000 K and a pressure of 4 atm). The non-equilibrium composition is characterized by departures from both thermal and chemical equilibrium. In thermal non-equilibrium process, the electron temperature (T e) is not equal to the heavy-particle temperature (T h), while for chemical non-equilibrium, a chemical kinetic model is adopted. In order to evaluate the reasonableness and reliability of the non-equilibrium composition, calculation methods for equilibrium composition based on Gibbs free energy minimization and kinetic composition in a one-temperature kinetic model are first considered. Based on the one-temperature kinetic model, a two-temperature kinetic model with the ratio T e/T h varying as a function of the logarithm of electron density ratio (n e/n\\text{e}\\max ) was established. In this model, T* is introduced to allow a smooth transition between T h and T e and to determine the temperatures for the rate constants. The initial composition in the kinetic models is obtained from the asymptotic composition as infinite time is approached at 12 000 K. The molar fractions of neutral particles and ions in the two-temperature kinetic model are consistent with the equilibrium composition and the composition obtained from the one-temperature kinetic model above 10 000 K, while significant differences appear below 10 000 K. Based on the dependence of the particle distributions on temperature in the two-temperature kinetic model, three temperature ranges, and the dominant particles and reactions in the respective ranges, are determined. The full model is then simplified into three models and the accuracy of the simplified models is assessed. The simplified models reduce the number of species and

  16. Degradation kinetics and mechanisms of phenol in photo-Fenton process

    Institute of Scientific and Technical Information of China (English)

    何锋; 雷乐成

    2004-01-01

    Phenol degradation in photochemically enhanced Fenton process was investigated in this work. UV-VIS spectra of phenol degradation showed the difference between photo-Fenton process and UV/H2O2, which is a typical hydroxyl radical process. A possible pathway diagram for phenol degradation in photo-Fenton process was proposed, and a mathematical model for chemical oxygen demand (COD) removal was developed. Operating parameters such as dosage of H2O2 and ferrous ions, pH, suitable carrier gas were found to impact the removal of COD significantly. The results and analysis of kinetic parameters calculated from the kinetic model showed that complex degradation of phenol was the main pathway for removal of COD; while hydroxyl radicals acted weakly in the photo-Fenton degradation of phenol.

  17. Fructose-catalyzed synthesis of tetrahydrobenzo[b]pyran derivatives:Investigation of kinetics and mechanism

    Institute of Scientific and Technical Information of China (English)

    Sayyedeh Shadfar Pourpanah; Mehdi Shahraki

    2015-01-01

    Fructose was used as an efficient catalyst for three-component condensation reactions of aryl alde-hydes, malononitrile, and dimedone in a mixture of EtOH and H2O as green solvents. The advantages of this method are a short reaction time, high yields, low cost, easy accesses, and simple work-up. The mechanism of the synthesis of a derivative of 4H-tetrahydrobenzo[b]pyran was clarified using spectroscopic kinetic methods. The activation energy (Ea = 65.34 kJ/mol) and related kinetic pa-rameters (ΔG‡ = 69.14 kJ/mol, ΔS‡ = 20.99 J/(mol·K), and ΔH‡ = 62.89 kJ/mol) were calculated, based on the effects of temperature, concentration, and solvent. The first step in the proposed mechanism was identified as the rate-determining step (k1), based on the steady-state approxima-tion.

  18. Kinetics and Mechanism of the Exothermic First-stage Decomposition Reaction of Dinitroglycoluril

    Institute of Scientific and Technical Information of China (English)

    ZHAO,Feng-Qi(赵凤起); HU,Rong-Zu(胡荣祖); CHEN,Pei(陈沛); LUO,Yang(罗阳); GAO,Sheng-Li(高胜利); SONG,Ji-Rong(宋纪蓉); SHI,Qi-Zhen(史启祯)

    2004-01-01

    Under linear temperature increase condition, the thermal behavior, mechanism and kinetic parameters of the exothermic decomposition reaction of the title compound have been studied by means of DSC and IR. The initial stage of the mechanism was proposed. The empirical kinetic model function in differential form, apparent activation energy and pre-exponential constant of the exothermic decomposition reaction are α 0.526, 207.0 kJ·mol-1 and 1018.49 s-1, respectively. The critical temperature of thermal explosion of the compound is 252.87 ℃. The values of △S≠, △H≠ and △G≠ of the reaction are 128.4 J·mol-1·K-1, 218.9 kJ·mol-1 and 152.7 kJ·mol-1, respectively.

  19. Chemical dynamics in the gas phase: Time-dependent quantum mechanics of chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

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

    1993-12-01

    A major goal of this research is to obtain an understanding of the molecular reaction dynamics of three and four atom chemical reactions using numerically accurate quantum dynamics. This work involves: (i) the development and/or improvement of accurate quantum mechanical methods for the calculation and analysis of the properties of chemical reactions (e.g., rate constants and product distributions), and (ii) the determination of accurate dynamical results for selected chemical systems, which allow one to compare directly with experiment, determine the reliability of the underlying potential energy surfaces, and test the validity of approximate theories. This research emphasizes the use of recently developed time-dependent quantum mechanical methods, i.e. wave packet methods.

  20. Kinetics and mechanism of sphalerite leaching by sodium nitrate in sulphuric acid solution

    OpenAIRE

    Sokić M.; Marković B.; Matković V.; Živković D.; Štrbac N.; Stojanović J.

    2012-01-01

    Interest for application of hydrometallurgical processes in a processing of complex sulphide ores and concentrates has increased in recent years. Their application provides better metal recoveries and reduced emission of gaseous and toxic ageneses in the environment. The kinetics and mechanism of sphalerite leaching from complex sulphide concentrate with sulphuric acid and sodium nitrate solution at standard conditions was presented in this paper. The influences of temperature and time ...

  1. The kinetic mechanism of wild-type and mutant mouse dihydrofolate reductases.

    Science.gov (United States)

    Thillet, J; Adams, J A; Benkovic, S J

    1990-05-29

    A kinetic mechanism is presented for mouse dihydrofolate reductase that predicts all the steady-state parameters and full time-course kinetics. This mechanism was derived from association and dissociation rate constants and pre-steady-state transients by using stopped-flow fluorescence and absorbance measurements. The major features of this kinetic mechanism are as follows: (1) the two native enzyme conformers, E1 and E2, bind ligands with varying affinities although only one conformer, E1, can support catalysis in the forward direction, (2) tetrahydrofolate dissociation is the rate-limiting step under steady-state turnover at low pH, and (3) the pH-independent rate of hydride transfer from NADPH to dihydrofolate is fast (khyd = 9000 s-1) and favorable (Keq = 100). The overall mechanism is similar in form to the Escherichia coli kinetic scheme (Fierke et al., 1987), although several differences are observed: (1) substrates and products predominantly bind the same form of the E. coli enzyme, and (2) the hydride transfer rate from NADPH to either folate or dihydrofolate is considerably faster for the mouse enzyme. The role of Glu-30 (Asp-27 in E. coli) in mouse DHFR has also been examined by using site-directed mutagenesis as a potential source of these differences. While aspartic acid is strictly conserved in all bacterial DHFRs, glutamic acid is conserved in all known eucaryotes. The two major effects of substituting Asp for Glu-30 in the mouse enzyme are (1) a decreased rate of folate reduction and (2) an increased rate of hydride transfer from NADPH to dihydrofolate.(ABSTRACT TRUNCATED AT 250 WORDS)

  2. Final Report: Molecular mechanisms and kinetics of microbial anaerobic nitrate-dependent U(IV) and Fe(II) oxidation

    Energy Technology Data Exchange (ETDEWEB)

    O' Day, Peggy A. [Univ. of California, Merced, CA (United States); Asta, Maria P. [Univ. of California, Merced, CA (United States); Kanematsu, Masakazu [Univ. of California, Merced, CA (United States); Beller, Harry [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Zhou, Peng [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Steefel, Carl [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2015-02-27

    In this project, we combined molecular genetic, spectroscopic, and microscopic techniques with kinetic and reactive transport studies to describe and quantify biotic and abiotic mechanisms underlying anaerobic, nitrate-dependent U(IV) and Fe(II) oxidation, which influences the long-term efficacy of in situ reductive immobilization of uranium at DOE sites. In these studies, Thiobacillus denitrificans, an autotrophic bacterium that catalyzes anaerobic U(IV) and Fe(II) oxidation, was used to examine coupled oxidation-reduction processes under either biotic (enzymatic) or abiotic conditions in batch and column experiments with biogenically produced UIVO2(s). Synthesis and quantitative analysis of coupled chemical and transport processes were done with the reactive transport modeling code Crunchflow. Research focused on identifying the primary redox proteins that catalyze metal oxidation, environmental factors that influence protein expression, and molecular-scale geochemical factors that control the rates of biotic and abiotic oxidation.

  3. Kinetic gating mechanism of DNA damage recognition by Rad4/XPC

    Science.gov (United States)

    Chen, Xuejing; Velmurugu, Yogambigai; Zheng, Guanqun; Park, Beomseok; Shim, Yoonjung; Kim, Youngchang; Liu, Lili; van Houten, Bennett; He, Chuan; Ansari, Anjum; Min, Jung-Hyun

    2015-01-01

    The xeroderma pigmentosum C (XPC) complex initiates nucleotide excision repair by recognizing DNA lesions before recruiting downstream factors. How XPC detects structurally diverse lesions embedded within normal DNA is unknown. Here we present a crystal structure that captures the yeast XPC orthologue (Rad4) on a single register of undamaged DNA. The structure shows that a disulphide-tethered Rad4 flips out normal nucleotides and adopts a conformation similar to that seen with damaged DNA. Contrary to many DNA repair enzymes that can directly reject non-target sites as structural misfits, our results suggest that Rad4/XPC uses a kinetic gating mechanism whereby lesion selectivity arises from the kinetic competition between DNA opening and the residence time of Rad4/XPC per site. This mechanism is further supported by measurements of Rad4-induced lesion-opening times using temperature-jump perturbation spectroscopy. Kinetic gating may be a general mechanism used by site-specific DNA-binding proteins to minimize time-consuming interrogations of non-target sites.

  4. Precipitation kinetics and mechanical behavior in a solution treated and aged dual phase stainless steel

    Energy Technology Data Exchange (ETDEWEB)

    Badji, R., E-mail: riadbadji1@yahoo.fr [Welding and NDT Research Centre (CSC), B.P. 64, Cheraga (Algeria); Kherrouba, N.; Mehdi, B.; Cheniti, B. [Welding and NDT Research Centre (CSC), B.P. 64, Cheraga (Algeria); Bouabdallah, M. [LGSDS – ENP, 10, Avenue Hassan Badi, 16200 El Harrah, Alger (Algeria); Kahloun, C.; Bacroix, B. [LSPM – CNRS, Université Paris 13, 93430 Villetaneuse (France)

    2014-12-15

    The precipitation kinetics and the mechanical behavior in a solution treated and aged dual phase stainless steel (DSS) are investigated. X-ray diffraction, transmission and scanning electron microscopy techniques are used to characterize the microstructure and to identify its constituents. The precipitation kinetics analysis shows that the ferrite to σ phase transformation follows the modified Johnson Mehl Avrami (JMA) model containing an impingement parameter c that is adjusted to 0.3. Activation energies calculation leads to conclude that interface reaction is the main mechanism that controls the σ phase formation. Detailed analysis of the extent of the different tensile deformation domains reveals the significant contribution of both σ phase particles and dislocation accumulation to the strain hardening of the material. - Highlights: • The precipitation kinetics of the σ phase is affected by both soft and hard impingement phenomena. • Interface reaction is found to be the main mechanism that controls the ferrite to σ phase transformation. • Both σ phase particles and dislocation accumulation contribute to the strain hardening of the dual phase steel studied.

  5. Precipitation kinetics and mechanical behavior in a solution treated and aged dual phase stainless steel

    International Nuclear Information System (INIS)

    The precipitation kinetics and the mechanical behavior in a solution treated and aged dual phase stainless steel (DSS) are investigated. X-ray diffraction, transmission and scanning electron microscopy techniques are used to characterize the microstructure and to identify its constituents. The precipitation kinetics analysis shows that the ferrite to σ phase transformation follows the modified Johnson Mehl Avrami (JMA) model containing an impingement parameter c that is adjusted to 0.3. Activation energies calculation leads to conclude that interface reaction is the main mechanism that controls the σ phase formation. Detailed analysis of the extent of the different tensile deformation domains reveals the significant contribution of both σ phase particles and dislocation accumulation to the strain hardening of the material. - Highlights: • The precipitation kinetics of the σ phase is affected by both soft and hard impingement phenomena. • Interface reaction is found to be the main mechanism that controls the ferrite to σ phase transformation. • Both σ phase particles and dislocation accumulation contribute to the strain hardening of the dual phase steel studied

  6. Chemical reactions modulated by mechanical stress: extended Bell theory.

    Science.gov (United States)

    Konda, Sai Sriharsha M; Brantley, Johnathan N; Bielawski, Christopher W; Makarov, Dmitrii E

    2011-10-28

    A number of recent studies have shown that mechanical stress can significantly lower or raise the activation barrier of a chemical reaction. Within a common approximation due to Bell [Science 200, 618 (1978)], this barrier is linearly dependent on the applied force. A simple extension of Bell's theory that includes higher order corrections in the force predicts that the force-induced change in the activation energy will be given by -FΔR - ΔχF(2)∕2. Here, ΔR is the change of the distance between the atoms, at which the force F is applied, from the reactant to the transition state, and Δχ is the corresponding change in the mechanical compliance of the molecule. Application of this formula to the electrocyclic ring-opening of cis and trans 1,2-dimethylbenzocyclobutene shows that this extension of Bell's theory essentially recovers the force dependence of the barrier, while the original Bell formula exhibits significant errors. Because the extended Bell theory avoids explicit inclusion of the mechanical stress or strain in electronic structure calculations, it allows a computationally efficient characterization of the effect of mechanical forces on chemical processes. That is, the mechanical susceptibility of any reaction pathway is described in terms of two parameters, ΔR and Δχ, both readily computable at zero force.

  7. The Radical Pair Mechanism and the Avian Chemical Compass: Quantum Coherence and Entanglement

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yiteng [Purdue Univ., West Lafayette, IN (United States); Kais, Sabre [Purdue Univ., West Lafayette, IN (United States); Berman, Gennady Petrovich [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2015-02-02

    We review the spin radical pair mechanism which is a promising explanation of avian navigation. This mechanism is based on the dependence of product yields on 1) the hyperfine interaction involving electron spins and neighboring nuclear spins and 2) the intensity and orientation of the geomagnetic field. One surprising result is that even at ambient conditions quantum entanglement of electron spins can play an important role in avian magnetoreception. This review describes the general scheme of chemical reactions involving radical pairs generated from singlet and triplet precursors; the spin dynamics of the radical pairs; and the magnetic field dependence of product yields caused by the radical pair mechanism. The main part of the review includes a description of the chemical compass in birds. We review: the general properties of the avian compass; the basic scheme of the radical pair mechanism; the reaction kinetics in cryptochrome; quantum coherence and entanglement in the avian compass; and the effects of noise. We believe that the quantum avian compass can play an important role in avian navigation and can also provide the foundation for a new generation of sensitive and selective magnetic-sensing nano-devices.

  8. Adsorption treatment of oxide chemical mechanical polishing wastewater from a semiconductor manufacturing plant by electrocoagulation

    Energy Technology Data Exchange (ETDEWEB)

    Chou, Wei-Lung, E-mail: wlchou@sunrise.hk.edu.tw [Department of Safety, Health and Environmental Engineering, Hungkuang University, No. 34, Chung-Chie Road, Sha-Lu, Taichung 433, Taiwan (China); Wang, Chih-Ta [Department of Safety Health and Environmental Engineering, Chung Hwa University of Medical Technology, Tainan Hsien 717, Taiwan (China); Chang, Wen-Chun; Chang, Shih-Yu [Department of Safety, Health and Environmental Engineering, Hungkuang University, No. 34, Chung-Chie Road, Sha-Lu, Taichung 433, Taiwan (China)

    2010-08-15

    In this study, metal hydroxides generated during electrocoagulation (EC) were used to remove the chemical oxygen demand (COD) of oxide chemical mechanical polishing (oxide-CMP) wastewater from a semiconductor manufacturing plant by EC. Adsorption studies were conducted in a batch system for various current densities and temperatures. The COD concentration in the oxide-CMP wastewater was effectively removed and decreased by more than 90%, resulting in a final wastewater COD concentration that was below the Taiwan discharge standard (100 mg L{sup -1}). Since the processed wastewater quality exceeded the direct discharge standard, the effluent could be considered for reuse. The adsorption kinetic studies showed that the EC process was best described using the pseudo-second-order kinetic model at the various current densities and temperatures. The experimental data were also tested against different adsorption isotherm models to describe the EC process. The Freundlich adsorption isotherm model predictions matched satisfactorily with the experimental observations. Thermodynamic parameters, including the Gibbs free energy, enthalpy, and entropy, indicated that the COD adsorption of oxide-CMP wastewater on metal hydroxides was feasible, spontaneous and endothermic in the temperature range of 288-318 K.

  9. Adsorption treatment of oxide chemical mechanical polishing wastewater from a semiconductor manufacturing plant by electrocoagulation

    International Nuclear Information System (INIS)

    In this study, metal hydroxides generated during electrocoagulation (EC) were used to remove the chemical oxygen demand (COD) of oxide chemical mechanical polishing (oxide-CMP) wastewater from a semiconductor manufacturing plant by EC. Adsorption studies were conducted in a batch system for various current densities and temperatures. The COD concentration in the oxide-CMP wastewater was effectively removed and decreased by more than 90%, resulting in a final wastewater COD concentration that was below the Taiwan discharge standard (100 mg L-1). Since the processed wastewater quality exceeded the direct discharge standard, the effluent could be considered for reuse. The adsorption kinetic studies showed that the EC process was best described using the pseudo-second-order kinetic model at the various current densities and temperatures. The experimental data were also tested against different adsorption isotherm models to describe the EC process. The Freundlich adsorption isotherm model predictions matched satisfactorily with the experimental observations. Thermodynamic parameters, including the Gibbs free energy, enthalpy, and entropy, indicated that the COD adsorption of oxide-CMP wastewater on metal hydroxides was feasible, spontaneous and endothermic in the temperature range of 288-318 K.

  10. Mechanism and kinetics of 2-chlorophenol degradation in drinking water by photo-electrochemical synergic effect

    Institute of Scientific and Technical Information of China (English)

    SONG; Qiang; (宋; 强); QU; Jiuhui; (曲久辉)

    2003-01-01

    The synergic effect mechanism of photo-electrochemical oxidation is investigated in detail through reaction products and kinetics analysis in a photo-electric integral reactor with 2-chlorophenol (2-CP) as the model pollutant. A kinetics model is constructed for the combinatorial photo-electrochemical (CPE) degradation. A remarkable synergetic effect, which can significantly enhance the mineralization rate of the CPE process, is verified by the comparison of apparent kinetic constants. In the CPE process, complemental effects with multi-level and multi-pathway for pollutants degradation under our experimental conditions are speculated. It is proved that the degradation pathways are not only the simple summation of that of photolysis and electrolysis, but the formation of synergic effect through combination of several new acting approaches. The degradation efficiency is enhanced considerably by three factors, control of electrode poisoning by the UV irradiation, control of excitation and reaction trend of pollutants molecules by the UV irradiation, and control of activation effect and transfer trend by the oriented direct current (DC) electric field. An advanced oxidation system is set up through manifold of free radicals chain reactions in the CPE reactions, so that the aqueous organics can be mineralized fast and completely. It is proven by the kinetics analysis that the mineralization of organic pollutants is mainly attributed to the generation of very active hydroxyl radicals (OH@) in bulk solution from the CPE synergetic effect.

  11. RADICAL QUENCHING OF METHANE-AIR PREMIXED FLAME IN MICROREACTORS USING DETAILED CHEMICAL KINETICS

    Directory of Open Access Journals (Sweden)

    JUNJIE CHEN

    2015-10-01

    Full Text Available The steady hetero-/homogeneous combustion of lean methane-air mixtures in plane channel-flow microreactors was investigated numerically to elucidate the effects of wall material and initial sticking coefficient on radical quenching. Simulations were performed with a two-dimensional numerical model employing detailed reaction mechanisms to examine the interaction between heterogeneous and homogeneous reactions on platinum, alumina, quartz and copper. Comparisons among wall materials revealed that the wall chemical effect plays a vital role in the distribution of OH* radical. Homogeneous reaction of methane over platinum is significantly inhibited due to the rapid depletion of reactants on catalytic surfaces, rather than the radical adsorption. The inhibition of radical quenching on the surface of alumina is most pronounced. As the microreactor is smaller than the critical dimension of 0.7 mm, the wall chemical effect on flame characteristics becomes of great importance.

  12. Effects of chemical modifications of heme on kinetics of carbon monoxide binding to free home

    Energy Technology Data Exchange (ETDEWEB)

    Sono, M.; McCray, J.A.; Asakura, T.

    1977-11-10

    The rates of carbon monoxide recombination to six different kinds of chemically modified heme with various substituents at positions 2 and 4 have been studied in the protein-free state (free heme) by the laser flash photolysis method in a mixture of ethylene glycol and 0.02 N NaOH (80:20, v/v) (80% ethylene glycol). The carbon monoxide combination rate constants to the various free hemes obtained in 80% ethylene glycol at 22/sup 0/ were 1.4, 2.1, 2.1, 3.7, 4.5, and 6.4 x 10/sup 7/ M/sup -1/ s/sup -1/ for 2,4-diformyl-, spirographis (2-formyl-4-vinyl-), isospirographis (2-vinyl-4-formyl-) proto-(2,4-divinyl-), deutero-(2,4-dihydrogen-), and meso-(2,4-diethyl-), hemes, respectively. This order of increase in carbon monoxide combination rate constants for these hemes correlates exactly with decrease in electron attractivity of heme side chains (i.e., increase in pK/sub 3/, basicity of nitrogen base of prophyrin) and is completely opposite to that obtained for carbon monoxide binding to these hemes reconstituted with apomyoglobin. Contrary to the results for myoglobin, the two isomers of monoformyl-monovinylheme exhibited similar optical properties and the same combination rate constant indicating that the differences in the optical and kinetic results observed in myoglobin are due to different interactions of these isomeric hemes with protein.

  13. Peroxone mineralization of chemical oxygen demand for direct potable water reuse: Kinetics and process control.

    Science.gov (United States)

    Wu, Tingting; Englehardt, James D

    2015-04-15

    Mineralization of organics in secondary effluent by the peroxone process was studied at a direct potable water reuse research treatment system serving an occupied four-bedroom, four bath university residence hall apartment. Organic concentrations were measured as chemical oxygen demand (COD) and kinetic runs were monitored at varying O3/H2O2 dosages and ratios. COD degradation could be accurately described as the parallel pseudo-1st order decay of rapidly and slowly-oxidizable fractions, and effluent COD was reduced to below the detection limit (water, and a relationship is proposed and demonstrated to estimate the pseudo-first order rate constant for design purposes. At this O3/H2O2 mass ratio, ORP and dissolved ozone were found to be useful process control indicators for monitoring COD mineralization in secondary effluent. Moreover, an average second order rate constant for OH oxidation of secondary effluent organics (measured as MCOD) was found to be 1.24 × 10(7) ± 0.64 × 10(7) M(-1) S(-1). The electric energy demand of the peroxone process is estimated at 1.73-2.49 kW h electric energy for removal of one log COD in 1 m(3) secondary effluent, comparable to the energy required for desalination of medium strength seawater. Advantages/disadvantages of the two processes for municipal wastewater reuse are discussed.

  14. Peroxone mineralization of chemical oxygen demand for direct potable water reuse: Kinetics and process control.

    Science.gov (United States)

    Wu, Tingting; Englehardt, James D

    2015-04-15

    Mineralization of organics in secondary effluent by the peroxone process was studied at a direct potable water reuse research treatment system serving an occupied four-bedroom, four bath university residence hall apartment. Organic concentrations were measured as chemical oxygen demand (COD) and kinetic runs were monitored at varying O3/H2O2 dosages and ratios. COD degradation could be accurately described as the parallel pseudo-1st order decay of rapidly and slowly-oxidizable fractions, and effluent COD was reduced to below the detection limit (process control indicators for monitoring COD mineralization in secondary effluent. Moreover, an average second order rate constant for OH oxidation of secondary effluent organics (measured as MCOD) was found to be 1.24 × 10(7) ± 0.64 × 10(7) M(-1) S(-1). The electric energy demand of the peroxone process is estimated at 1.73-2.49 kW h electric energy for removal of one log COD in 1 m(3) secondary effluent, comparable to the energy required for desalination of medium strength seawater. Advantages/disadvantages of the two processes for municipal wastewater reuse are discussed. PMID:25704155

  15. Survey of high-enthalpy shock facilities in the perspective of radiation and chemical kinetics investigations

    Science.gov (United States)

    Reynier, Philippe

    2016-08-01

    This contribution is a survey of the capabilities of the main facilities, shock-tubes, shock-tunnels, expansion tubes and hot-shots that allow the experimental investigation of chemical kinetics and radiation of hypersonic flows encountered during atmospheric entry. At first, the capabilities of the main facilities available in Australia, Asia, Europe, and United States, have been surveyed using the available literature, and the specific use of each facility identified. The second step of the study consists in an analysis of each type of shock facility to identify their advantages and drawbacks. The main objective of this analysis is to support a trade-off for the selection of the type of facility to be developed in order to give Europe a ground test with the capabilities to support future exploration and sample return missions. The last point of the study has been to identify the experimental datasets related to the targeted application, and to select the most attractive for the validation of the future facility.

  16. On role of kinetic fluctuations in laminar-turbulent transition in chemically nonequilibrium boundary layer flows

    Science.gov (United States)

    Tumin, Anatoli

    2015-11-01

    Zavol'skii and Reutov (1983), Luchini (2008, 2010), Fedorov (2010, 2012, 2014) explored potential role of kinetic fluctuations (KF) in incompressible and calorically perfect gas boundary layer flows. The results indicate that role of KF is comparable with other disturbance sources in flight experiments and in quiet wind tunnels. The analysis is based on the Landau and Lifshitz (1957) concept of fluctuating hydrodynamics representing the dissipative fluxes as an average and fluctuating parts. We are extending analysis of the receptivity problem to the fluctuating dissipative fluxes in chemically reacting nonequilibrium boundary layer flows of binary mixtures. There are new terms in the energy, and the species equations. The species conservation equation includes the dissipative diffusion flux and the species generation due to dissociation. The momentum equation includes fluctuating stress tensor. The energy equation includes fluctuating heat flux, energy flux due to diffusion of the species, and fluctuating dissipative flux due to viscosity. The effects are compared for the cases stemming from constraints of the HTV project (Klentzman and Tumin, AIAA Paper 2013-2882). Supported by AFOSR.

  17. Decomposition kinetics of dimethyl methylphospate(chemical agent simulant) by supercritical water oxidation

    Institute of Scientific and Technical Information of China (English)

    Bambang VERIANSYAH; Jae-Duck KIM; Youn-Woo LEE

    2006-01-01

    Supercritical water oxidation (SCWO) has been drawing much attention due to effectively destroy a large variety of high-risk wastes resulting from munitions demilitarization and complex industrial chemical. An important design consideration in the development of supercritical water oxidation is the information of decomposition rate. In this paper, the decomposition rate of dimethyl methylphosphonate(DMMP), which is similar to the nerve agent VX and GB(Sarin) in its structure, was investigated under SCWO conditions. The experiments were performed in an isothermal tubular reactor with a H2O2 as an oxidant. The reaction temperatures were ranged from 398 to 633 ℃ at a fixed pressure of 24 MPa. The conversion of DMMP was monitored by analyzing total organic carbon (TOC) on the liquid effluent samples. It is found that the oxidative decomposition of DMMP proceeded rapidly and a high TOC decomposition up to 99.99% was obtained within 11 s at 555℃. On the basis of data derived from experiments, a global kinetic equation for the decomposition of DMMP was developed. The model predictions agreed well with the experimental data.

  18. pypk - A Python extension module to handle chemical kinetics in plasma physics modeling

    Directory of Open Access Journals (Sweden)

    2008-06-01

    Full Text Available PLASMAKIN is a package to handle physical and chemical data used in plasma physics modeling and to compute gas-phase and gas-surface kinetics data: particle production and loss rates, photon emission spectra and energy exchange rates. A large number of species properties and reaction types are supported, namely: gas or electron temperature dependent collision rate coefficients, vibrational and cascade levels, evaluation of branching ratios, superelastic and other reverse processes, three-body collisions, radiation imprisonment and photoelectric emission. Support of non-standard rate coefficient functions can be handled by a user-supplied shared library.

    The main block of the PLASMAKIN package is a Fortran module that can be included in an user's program or compiled as a shared library, libpk. pypk is a new addition to the package and provides access to libpk from Python programs. It is build on top of the ctypes foreign function library module and is prepared to work with several Fortran compilers. However pypk is more than a wrapper and provides its own classes and functions taking advantage of Python language characteristics. Integration with Python tools allows substantial productivity gains on program development and insight on plasma physics problems.

  19. An investigation of GPU-based stiff chemical kinetics integration methods

    CERN Document Server

    Curtis, Nicholas J; Sung, Chih-Jen

    2016-01-01

    A fifth-order implicit Runge-Kutta method and two fourth-order exponential integration methods equipped with Krylov subspace approximations were implemented for the GPU and paired with the analytical chemical kinetic Jacobian software pyJac. The performance of each algorithm was evaluated by integrating thermochemical state data sampled from stochastic partially stirred reactor simulations and compared with the commonly used CPU-based implicit integrator CVODE. We estimated that the implicit Runge-Kutta method running on a single GPU is equivalent to CVODE running on 12-38 CPU cores for integration of a single global integration time step of 1e-6 s with hydrogen and methane models. In the stiffest case studied---the methane model with a global integration time step of 1e-4 s---thread divergence and higher memory traffic significantly decreased GPU performance to the equivalent of CVODE running on approximately three CPU cores. The exponential integration algorithms performed more slowly than the implicit inte...

  20. Quantum Chemical and Kinetic Study on Polychlorinated Naphthalene Formation from 3-Chlorophenol Precursor.

    Science.gov (United States)

    Xu, Fei; Shi, Xiangli; Zhang, Qingzhu

    2015-01-01

    Polychlorinated naphthalenes (PCNs) are the smallest chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) and are often called dioxin-like compounds. Chlorophenols (CPs) are important precursors of PCN formation. In this paper, mechanistic and kinetic studies on the homogeneous gas-phase formation mechanism of PCNs from 3-CP precursor were investigated theoretically by using the density functional theory (DFT) method and canonical variational transition-state theory (CVT) with small curvature tunneling contribution (SCT). The reaction priority of different PCN formation pathways were disscussed. The rate constants of crucial elementary steps were deduced over a wide temperature range of 600-1200 K. The mechanisms were compared with the experimental observation and our previous works on the PCN formation from 2-CP and 4-CP. This study shows that pathways ended with Cl elimination are favored over those ended with H elimination from the 3-CP precursor. The formation potential of MCN is larger than that of DCN. The chlorine substitution pattern of monochlorophenols has a significant effect on isomer patterns and formation potential of PCN products. The results can be input into the environmental PCN controlling and prediction models as detailed parameters, which can be used to confirm the formation routes of PCNs, reduce PCN emission and establish PCN controlling strategies. PMID:26334273

  1. Quantum Chemical and Kinetic Study on Polychlorinated Naphthalene Formation from 3-Chlorophenol Precursor

    Directory of Open Access Journals (Sweden)

    Fei Xu

    2015-08-01

    Full Text Available Polychlorinated naphthalenes (PCNs are the smallest chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs and are often called dioxin-like compounds. Chlorophenols (CPs are important precursors of PCN formation. In this paper, mechanistic and kinetic studies on the homogeneous gas-phase formation mechanism of PCNs from 3-CP precursor were investigated theoretically by using the density functional theory (DFT method and canonical variational transition-state theory (CVT with small curvature tunneling contribution (SCT. The reaction priority of different PCN formation pathways were disscussed. The rate constants of crucial elementary steps were deduced over a wide temperature range of 600−1200 K. The mechanisms were compared with the experimental observation and our previous works on the PCN formation from 2-CP and 4-CP. This study shows that pathways ended with Cl elimination are favored over those ended with H elimination from the 3-CP precursor. The formation potential of MCN is larger than that of DCN. The chlorine substitution pattern of monochlorophenols has a significant effect on isomer patterns and formation potential of PCN products. The results can be input into the environmental PCN controlling and prediction models as detailed parameters, which can be used to confirm the formation routes of PCNs, reduce PCN emission and establish PCN controlling strategies.

  2. Quantum Chemical and Kinetic Study on Polychlorinated Naphthalene Formation from 3-Chlorophenol Precursor.

    Science.gov (United States)

    Xu, Fei; Shi, Xiangli; Zhang, Qingzhu

    2015-08-31

    Polychlorinated naphthalenes (PCNs) are the smallest chlorinated polycyclic aromatic hydrocarbons (Cl-PAHs) and are often called dioxin-like compounds. Chlorophenols (CPs) are important precursors of PCN formation. In this paper, mechanistic and kinetic studies on the homogeneous gas-phase formation mechanism of PCNs from 3-CP precursor were investigated theoretically by using the density functional theory (DFT) method and canonical variational transition-state theory (CVT) with small curvature tunneling contribution (SCT). The reaction priority of different PCN formation pathways were disscussed. The rate constants of crucial elementary steps were deduced over a wide temperature range of 600-1200 K. The mechanisms were compared with the experimental observation and our previous works on the PCN formation from 2-CP and 4-CP. This study shows that pathways ended with Cl elimination are favored over those ended with H elimination from the 3-CP precursor. The formation potential of MCN is larger than that of DCN. The chlorine substitution pattern of monochlorophenols has a significant effect on isomer patterns and formation potential of PCN products. The results can be input into the environmental PCN controlling and prediction models as detailed parameters, which can be used to confirm the formation routes of PCNs, reduce PCN emission and establish PCN controlling strategies.

  3. A comparative study of the chemical kinetics of methyl and ethyl propanoate

    KAUST Repository

    Farooq, Aamir

    2014-10-01

    High temperature pyrolysis of methyl propanoate (CH3CH 2C(O)OCH3) and ethyl propanoate (CH3CH 2C(O)OCH2CH3) was studied behind reflected shock waves at temperatures of 1250-1750 K and pressure of 1.5 atm. Species time-histories were recorded for CO, CO2, C2H4, and H2O using laser absorption methods over a test time of 1 ms. Pyrolysis of methyl propanoate (MP) appears to be faster than that of ethyl propanoate (EP) under the present experimental conditions, where CO and CO 2 reach their plateau values faster for MP at a specific temperature and fuel concentration. Higher plateau values are reached for CO in case of MP while the CO2 levels are similar for the two ester fuels. Ethylene production is larger for EP due to the presence of six-centered ring elimination reaction that produces ethylene and propanoic acid. Very little H2O is produced during MP pyrolysis in contrast with appreciable H2O production from EP. Sensitivity and rate-of-production analyses were carried out to identify key reactions that affect the measured species profiles. Previous kinetic mechanisms of Yang et al. (2011) [1,2] and Metcalf et al. (2009, 2007) [3,4] were used as base models and then refined to propose a new MP/EP pyrolysis mechanism. © 2014 Elsevier Ltd. All rights reserved.

  4. Kinetic, Thermodynamic, and Structural Insight into the Mechanism of Phosphopantetheine Adenylyltransferase from Mycobacterium tuberculosis

    Energy Technology Data Exchange (ETDEWEB)

    Wubben, Thomas J.; Mesecar, Andrew D. (Purdue); (UIC)

    2012-05-29

    Phosphopantetheine adenylyltransferase (PPAT) catalyzes the penultimate step in the coenzyme A (CoA) biosynthetic pathway, reversibly transferring an adenylyl group from ATP to 4'-phosphopantetheine (PhP) to form dephosphocoenzyme A. This reaction sits at the branch point between the de novo pathway and the salvage pathway, and has been shown to be a rate-limiting step in the biosynthesis of CoA. Importantly, bacterial and mammalian PPATs share little sequence homology, making the enzyme a potential target for antibiotic development. A series of steady-state kinetic, product inhibition, and direct binding studies with Mycobacterium tuberculosis PPAT (MtPPAT) was conducted and suggests that the enzyme utilizes a nonrapid-equilibrium random bi-bi mechanism. The kinetic response of MtPPAT to the binding of ATP was observed to be sigmoidal under fixed PhP concentrations, but substrate inhibition was observed at high PhP concentrations under subsaturating ATP concentrations, suggesting a preferred pathway to ternary complex formation. Negative cooperativity in the kinetic response of MtPPAT to PhP binding was observed under certain conditions and confirmed thermodynamically by isothermal titration calorimetry, suggesting the formation of an asymmetric quaternary structure during sequential ligation of substrates. Asymmetry in binding was also observed in isothermal titration calorimetry experiments with dephosphocoenzyme A and CoA. X-ray structures of MtPPAT in complex with PhP and the nonhydrolyzable ATP analogue adenosine-5'-[({alpha},{beta})-methyleno]triphosphate were solved to 1.57 {angstrom} and 2.68 {angstrom}, respectively. These crystal structures reveal small conformational changes in enzyme structure upon ligand binding, which may play a role in the nonrapid-equilibrium mechanism. We suggest that the proposed kinetic mechanism and asymmetric character in MtPPAT ligand binding may provide a means of reaction and pathway regulation in addition to that

  5. Coupling between chemical degradation and mechanical behaviour of leached concrete

    International Nuclear Information System (INIS)

    This work is in the context of the long term behavior of concrete employed in radioactive waste disposal. The objective is to study the coupled chemo-mechanical modelling of concrete. In the first part of this contribution, experimental investigations are described where the effects of the calcium leaching process of concrete on its mechanical properties are highlighted. An accelerated method has been chosen to perform this leaching process by using an ammonium nitrate solution. In the second part, we present a coupled phenomenological chemo-mechanical model that represents the degradation of concrete materials. On one hand, the chemical behavior is described by the simplified calcium leaching approach of cement paste and mortar. Then a homogenization approach using the asymptotic development is presented to take into account the influence of the presence of aggregates in concrete. And on the other hand, the mechanical part of the modelling is given. Here continuum damage mechanics is used to describe the mechanical degradation of concrete. The growth of inelastic strains observed during the mechanical tests is describes by means of a plastic like model. The model is established on the basis of the thermodynamics of irreversible processes framework. The coupled nonlinear problem at hand is addressed within the context of the finite element method. Finally, numerical simulations are compared with the experimental results for validation. (author)

  6. Kinetics and Mechanisms of Chalcopyrite Dissolution at Controlled Redox Potential of 750 mV in Sulfuric Acid Solution

    Directory of Open Access Journals (Sweden)

    Yubiao Li

    2016-08-01

    Full Text Available To better understand chalcopyrite leach mechanisms and kinetics, for improved Cu extraction during hydrometallurgical processing, chalcopyrite leaching has been conducted at solution redox potential 750 mV, 35–75 °C, and pH 1.0 with and without aqueous iron addition, and pH 1.5 and 2.0 without aqueous iron addition. The activation energy (Ea values derived indicate chalcopyrite dissolution is initially surface chemical reaction controlled, which is associated with the activities of Fe3+ and H+ with reaction orders of 0.12 and −0.28, respectively. A surface diffusion controlled mechanism is proposed for the later leaching stage with correspondingly low Ea values. Surface analyses indicate surface products (predominantly Sn2− and S0 did not inhibit chalcopyrite dissolution, consistent with the increased surface area normalised leach rate during the later stage. The addition of aqueous iron plays an important role in accelerating Cu leaching rates, especially at lower temperature, primarily by reducing the length of time of the initial surface chemical reaction controlled stage.

  7. Kinetics and mechanism of sphalerite leaching by sodium nitrate in sulphuric acid solution

    Directory of Open Access Journals (Sweden)

    Sokić M.

    2012-01-01

    Full Text Available Interest for application of hydrometallurgical processes in a processing of complex sulphide ores and concentrates has increased in recent years. Their application provides better metal recoveries and reduced emission of gaseous and toxic ageneses in the environment. The kinetics and mechanism of sphalerite leaching from complex sulphide concentrate with sulphuric acid and sodium nitrate solution at standard conditions was presented in this paper. The influences of temperature and time on the leaching degree of zinc were investigated and kinetic analysis of the process was accomplished. With temperature increasing from 60 to 90°C, the zinc leaching increased from 25.23% to 71.66% after 2 hours, i.e. from 59.40% to 99.83% after 4 hours. The selected kinetic model indicated that the diffusion through the product layer was the rate-controlling step during the sphalerite leaching. The activation energy was determined to be 55 kJ/mol in the temperature range 60-90°C. XRD, light microscopy and SEM/EDX analyses of the complex concentrate and leach residue confirmed formation of elemental sulphur and diffusion-controlled leaching mechanism.

  8. Structural and kinetic insights into the mechanism of 5-hydroxyisourate hydrolase from Klebsiella pneumoniae

    Energy Technology Data Exchange (ETDEWEB)

    French, Jarrod B.; Ealick, Steven E., E-mail: see3@cornell.edu [Cornell University, Ithaca, NY 14853-1301 (United States)

    2011-08-01

    The crystal structure of 5-hydroxyisourate hydrolase from K. pneumoniae and the steady-state kinetic parameters of the native enzyme as well as several mutants provide insights into the catalytic mechanism of this enzyme and the possible roles of the active-site residues. The stereospecific oxidative degradation of uric acid to (S)-allantoin has recently been demonstrated to proceed via two unstable intermediates and requires three separate enzymatic reactions. The second step of this reaction, the conversion of 5-hydroxyisourate (HIU) to 2-oxo-4-hydroxy-4-carboxy-5-ureidoimidazoline, is catalyzed by HIU hydrolase (HIUH). The high-resolution crystal structure of HIUH from the opportunistic pathogen Klebsiella pneumoniae (KpHIUH) has been determined. KpHIUH is a homotetrameric protein that, based on sequence and structural similarity, belongs to the transthyretin-related protein family. In addition, the steady-state kinetic parameters for this enzyme and four active-site mutants have been measured. These data provide valuable insight into the functional roles of the active-site residues. Based upon the structural and kinetic data, a mechanism is proposed for the KpHIUH-catalyzed reaction.

  9. Modeling Chemical Mechanical Polishing with Couple Stress Fluids

    Institute of Scientific and Technical Information of China (English)

    张朝辉; 雒建斌; 温诗铸

    2004-01-01

    Chemical mechanical polishing (CMP) is a manufacturing process used to achieve high levels of global and local planarity.Currently, the slurries used in CMP usually contain nanoscale particles to accelerate the removal ratio and to optimize the planarity, whose rheological properties can no longer be accurately modeled with Newtonian fluids.The Reynolds equation, including the couple stress effects, was derived in this paper.The equation describes the mechanism to solve the CMP lubrication equation with the couple stress effects.The effects on load and moments resulting from the various parameters, such as pivot height, roll angle, and pitch angle, were subsequently simulated.The results show that the couple stress can provide higher load and angular moments.This study sheds some lights into the mechanism of the CMP process.

  10. The Effects of Consistent Chemical Kinetics Calculations on the Pressure-Temperature Profiles and Emission Spectra of Hot Jupiters

    CERN Document Server

    Drummond, Benjamin; Baraffe, Isabelle; Amundsen, David S; Mayne, Nathan J; Venot, Olivia; Goyal, Jayesh

    2016-01-01

    In this work we investigate the impact of calculating non-equilibrium chemical abundances consistently with the temperature structure for the atmospheres of highly-irradiated, close-in gas giant exoplanets. Chemical kinetics models have been widely used in the literature to investigate the chemical compositions of hot Jupiter atmospheres which are expected to be driven away from chemical equilibrium via processes such as vertical mixing and photochemistry. All of these models have so far used pressure--temperature (P-T) profiles as fixed model input. This results in a decoupling of the chemistry from the radiative and thermal properties of the atmosphere, despite the fact that in nature they are intricately linked. We use a one-dimensional radiative-convective equilibrium model, ATMO, which includes a sophisticated chemistry scheme to calculate P-T profiles which are fully consistent with non-equilibrium chemical abundances, including vertical mixing and photochemistry. Our primary conclusion is that, in case...

  11. Kinetics and fracture resistance of lithiated silicon nanostructure pairs controlled by their mechanical interaction

    Science.gov (United States)

    Lee, Seok Woo; Lee, Hyun-Wook; Ryu, Ill; Nix, William D.; Gao, Huajian; Cui, Yi

    2015-06-01

    Following an explosion of studies of silicon as a negative electrode for Li-ion batteries, the anomalous volumetric changes and fracture of lithiated single Si particles have attracted significant attention in various fields, including mechanics. However, in real batteries, lithiation occurs simultaneously in clusters of Si in a confined medium. Hence, understanding how the individual Si structures interact during lithiation in a closed space is necessary. Here, we demonstrate physical and mechanical interactions of swelling Si structures during lithiation using well-defined Si nanopillar pairs. Ex situ SEM and in situ TEM studies reveal that compressive stresses change the reaction kinetics so that preferential lithiation occurs at free surfaces when the pillars are mechanically clamped. Such mechanical interactions enhance the fracture resistance of lithiated Si by lessening the tensile stress concentrations in Si structures. This study will contribute to improved design of Si structures at the electrode level for high-performance Li-ion batteries.

  12. LSENS, a general chemical kinetics and sensitivity analysis code for homogeneous gas-phase reactions. 2: Code description and usage

    Science.gov (United States)

    Radhakrishnan, Krishnan; Bittker, David A.

    1994-01-01

    LSENS, the Lewis General Chemical Kinetics Analysis Code, has been developed for solving complex, homogeneous, gas-phase chemical kinetics problems and contains sensitivity analysis for a variety of problems, including nonisothermal situations. This report is part 2 of a series of three reference publications that describe LSENS, provide a detailed guide to its usage, and present many example problems. Part 2 describes the code, how to modify it, and its usage, including preparation of the problem data file required to execute LSENS. Code usage is illustrated by several example problems, which further explain preparation of the problem data file and show how to obtain desired accuracy in the computed results. LSENS is a flexible, convenient, accurate, and efficient solver for chemical reaction problems such as static system; steady, one-dimensional, inviscid flow; reaction behind incident shock wave, including boundary layer correction; and perfectly stirred (highly backmixed) reactor. In addition, the chemical equilibrium state can be computed for the following assigned states: temperature and pressure, enthalpy and pressure, temperature and volume, and internal energy and volume. For static problems the code computes the sensitivity coefficients of the dependent variables and their temporal derivatives with respect to the initial values of the dependent variables and/or the three rate coefficient parameters of the chemical reactions. Part 1 (NASA RP-1328) derives the governing equations describes the numerical solution procedures for the types of problems that can be solved by lSENS. Part 3 (NASA RP-1330) explains the kinetics and kinetics-plus-sensitivity-analysis problems supplied with LSENS and presents sample results.

  13. ′ Precipitation and Growth Kinetics in Mechanically Alloyed Ni–Al

    Directory of Open Access Journals (Sweden)

    QingXin Tang

    2011-01-01

    Full Text Available The precipitation and growth kinetics of γ′ precipitates, which are strengthening factors in Ni-base oxide dispersion strengthened (ODS superalloys, were investigated. The cuboidal-type γ′ precipitates are formed in conventional arc-melted Ni–Al alloys, whereas spherical-type precipitates are formed in the mechanically alloyed (MAed specimens. The morphology is controlled by a lattice misfit between the γ′ precipitates and the matrix at the aging temperature of 800°C. The growth kinetics of the γ′ precipitates can be followed by Ostwald ripening. The Arrhenius plot yielded a lower activation energy for the solute atom diffusion in MAed specimens, which is attributed to their high dislocation density and nanosized grains.

  14. Kinetics and mechanism of oxidation of aliphatic alcohols by tetrabutylammonium tribromide

    Indian Academy of Sciences (India)

    Manju Baghmar; Pradeep K Sharma

    2001-04-01

    Oxidation of nine primary aliphatic alcohols by tetrabutylammonium tribromide (TBATB) in aqueous acetic acid leads to the formation of the corresponding aldehydes. The reaction is first order with respect to TBATB. Michaelis-Menten type kinetics is observed with respect to alcohols. The reaction failed to induce the polymerization of acrylonitrile. Tetrabutylammonium chloride has no effect on the reaction rate. The proposed reactive oxidizing species is the tribromide ion. The oxidation of [1,1-2H2]ethanol exhibits a substantial kinetic isotope effect. The effect of solvent composition indicates that the rate increases with increase in the polarity of the solvent. The reaction is susceptible to both polar and steric effects of substituents. A mechanism involving transfer of a hydride ion in the ratedetermining step has been proposed.

  15. Kinetics and Mechanism of Adsorption of Phosphate on Fluorine-containing Calcium Silicate

    Institute of Scientific and Technical Information of China (English)

    ZHU Xinhua; ZHANG Zhao; SHEN Jun

    2016-01-01

    The nanowires-reticulated calcium silicate with a speciifc surface area more than 100 m2/g was prepared by a hydrothermal process using hydrated lime (Ca(OH)2, HL) and silica containing soluble lfuoride, which was a by-product of lfuorine industry, and the soluble lfuoride in raw silica was ifxed as CaSiF6 at the same time. The kinetic characteristics and mechanism of adsorbing phosphate by lfuorine-containing calcium silicate were investigated in the experiments of phosphorus (P) removal from aqueous solution. The results show that the prepared lfuorine-containing calcium silicate has excellent performance for adsorbing phosphate, the adsorption process appears to follow pseudo-second-order reaction kinetics and the process is mainly controlled by chemisorption. The product resulted from P adsorption is mainly composed of hydroxyapatite (HAP) and lfuorapatite (FAP), which are further used as adsorbents of heavy metal ion Cd2+ in aqueous solution and display excellent performance.

  16. Structural and kinetic insights into the mechanism of 5-hydroxyisourate hydrolase from Klebsiella pneumoniae

    Energy Technology Data Exchange (ETDEWEB)

    French, Jarrod B.; Ealick, Steven E. (Cornell)

    2011-07-19

    The stereospecific oxidative degradation of uric acid to (S)-allantoin has recently been demonstrated to proceed via two unstable intermediates and requires three separate enzymatic reactions. The second step of this reaction, the conversion of 5-hydroxyisourate (HIU) to 2-oxo-4-hydroxy-4-carboxy-5-ureidoimidazoline, is catalyzed by HIU hydrolase (HIUH). The high-resolution crystal structure of HIUH from the opportunistic pathogen Klebsiella pneumoniae (KpHIUH) has been determined. KpHIUH is a homotetrameric protein that, based on sequence and structural similarity, belongs to the transthyretin-related protein family. In addition, the steady-state kinetic parameters for this enzyme and four active-site mutants have been measured. These data provide valuable insight into the functional roles of the active-site residues. Based upon the structural and kinetic data, a mechanism is proposed for the KpHIUH-catalyzed reaction.

  17. Effect and kinetic mechanism of ultrasonic vibration on solidification of 7050 aluminum alloy

    Directory of Open Access Journals (Sweden)

    Ripeng Jiang

    2014-07-01

    Full Text Available The work described in this paper dealt with the effect of ultrasonic vibration on the solidification of 7050 aluminum alloy. Two experiments were carried out through introducing ultrasound into the semi-continuous direct-chill (DC casting of aluminum alloy and into alloy solidifying in a crucible, respectively. Results show that ultrasonic vibration can refine grains in the whole cross-section of a billet in the first experiment and is able to increase the cooling rate within the temperature range from 625 °C to 590 °C in the other one. The mechanism of particle resonance caused by ultrasonic vibration was illustrated on the basis of theoretical analysis of the kinetics and energy conversion during the solidification. It is demonstrated that the kinetic energy of resonant particles are mainly from the latent heat energy of solidification, which can shorten the cooling time, inhibit the crystal growth and then lead to the grain refinement.

  18. A Chemical Kinetic Modeling Study of the Effects of Oxygenated Hydrocarbons on Soot Emissions from Diesel Engines

    Energy Technology Data Exchange (ETDEWEB)

    Westbrook, C K; Pitz, W J; Curran, H J

    2005-11-14

    A detailed chemical kinetic modeling approach is used to examine the phenomenon of suppression of sooting in diesel engines by addition of oxygenated hydrocarbon species to the fuel. This suppression, which has been observed experimentally for a few years, is explained kinetically as a reduction in concentrations of soot precursors present in the hot products of a fuel-rich diesel ignition zone when oxygenates are included. Oxygenates decrease the overall equivalence ratio of the igniting mixture, producing higher ignition temperatures and more radical species to consume more soot precursor species, leading to lower soot production. The kinetic model is also used to show how different oxygenates, ester structures in particular, can have different soot-suppression efficiencies due to differences in molecular structure of the oxygenated species.

  19. An integrated fingerprinting and kinetic approach to accelerated shelf-life testing of chemical changes in thermally treated carrot puree.

    Science.gov (United States)

    Kebede, Biniam T; Grauwet, Tara; Magpusao, Johannes; Palmers, Stijn; Michiels, Chris; Hendrickx, Marc; Loey, Ann Van

    2015-07-15

    To have a better understanding of chemical reactions during shelf-life, an integrated analytical and engineering toolbox: "fingerprinting-kinetics" was used. As a case study, a thermally sterilised carrot puree was selected. Sterilised purees were stored at four storage temperatures as a function of time. Fingerprinting enabled selection of volatiles clearly changing during shelf-life. Only these volatiles were identified and studied further. Next, kinetic modelling was performed to investigate the suitability of these volatiles as quality indices (markers) for accelerated shelf-life testing (ASLT). Fingerprinting enabled selection of terpenoids, phenylpropanoids, fatty acid derivatives, Strecker aldehydes and sulphur compounds as volatiles clearly changing during shelf-life. The amount of Strecker aldehydes increased during storage, whereas the rest of the volatiles decreased. Out of the volatiles, based on the applied kinetic modelling, myristicin, α-terpinolene, β-pinene, α-terpineol and octanal were identified as potential markers for ASLT. PMID:25722143

  20. Kinetic Reaction Mechanism of Sinapic Acid Scavenging NO2 and OH Radicals: A Theoretical Study

    Science.gov (United States)

    Lu, Yang; Wang, AiHua; Shi, Peng; Zhang, Hui; Li, ZeSheng

    2016-01-01

    The mechanism and kinetics underlying reactions between the naturally-occurring antioxidant sinapic acid (SA) and the very damaging ·NO2 and ·OH were investigated through the density functional theory (DFT). Two most possible reaction mechanisms were studied: hydrogen atom transfer (HAT) and radical adduct formation (RAF). Different reaction channels of neutral and anionic sinapic acid (SA-) scavenging radicals in both atmosphere and water medium were traced independently, and the thermodynamic and kinetic parameters were calculated. We find the most active site of SA/SA- scavenging ·NO2 and ·OH is the –OH group in benzene ring by HAT mechanism, while the RAF mechanism for SA/SA- scavenging ·NO2 seems thermodynamically unfavorable. In water phase, at 298 K, the total rate constants of SA eliminating ·NO2 and ·OH are 1.30×108 and 9.20×109 M-1 S-1 respectively, indicating that sinapic acid is an efficient scavenger for both ·NO2 and ·OH. PMID:27622460

  1. Crystallization mechanism and kinetics of mayenite glass prepared by aerodynamic levitation method

    Science.gov (United States)

    Duan, Jiao; Liu, Yan; Gu, Yanjing; Pan, Xiuhong; Zheng, Xiaojie; Wang, Wei; Yu, Huimei; Yu, Jianding

    2016-05-01

    The mayenite glass with a wide high-temperature stability (ΔT=131∘C) was innovatively synthesized by the aerodynamic levitation (ADL) containerless technique without conventional glass-forming addictives. The crystallization mechanism and kinetics of mayenite glass were studied by X-ray diffraction (XRD), scaning electron microscopy (SEM), Raman spectra and differential scanning calorimetry (DSC) analysis. The crystallization mechanism study revealed that structure and morphology mainly evolved near the crystallization peak temperature by the networking process of isolated AlO4 tetrahedra units, resulting in the growth mechanism changing from “two-dimensional” to “three-dimensional”. Crystallization kinetics calculations based on the non-isothermal Matusita model indicated that the activation energy for the crystallization of mayenite glass was 844kJṡmol‑1. The calculated growth morphology parameters (m and n) also confirmed the surface crystallization along with bulk crystallization mechanism for the mayenite glass. This present study supplied a thermal-physical understanding about the crystallization of mayenite glass, which could be further applied in the exploitation of glass/glass-ceramics in the CaO-Al2O3 binary system.

  2. Kinetic isotope effects support the twisted amide mechanism of Pin1 peptidyl-prolyl isomerase.

    Science.gov (United States)

    Mercedes-Camacho, Ana Y; Mullins, Ashley B; Mason, Matthew D; Xu, Guoyan G; Mahoney, Brendan J; Wang, Xingsheng; Peng, Jeffrey W; Etzkorn, Felicia A

    2013-11-01

    The Pin1 peptidyl-prolyl isomerase catalyzes isomerization of pSer/pThr-Pro motifs in regulating the cell cycle. Peptide substrates, Ac-Phe-Phe-phosphoSer-Pro-Arg-p-nitroaniline, were synthesized in unlabeled form, and with deuterium-labeled Ser-d3 and Pro-d7 amino acids. Kinetic data were collected as a function of Pin1 concentration to measure kinetic isotope effects (KIEs) on catalytic efficiency (kcat/Km). The normal secondary (2°) KIE value measured for the Ser-d3 substrate (kH/kD = 1.6 ± 0.2) indicates that the serine carbonyl does not rehybridize from sp(2) to sp(3) in the rate-determining step, ruling out a nucleophilic addition mechanism. The normal 2° KIE can be explained by hyperconjugation between Ser α-C-H/D and C═O and release of steric strain upon rotation of the amide bond from cis to syn-exo. The inverse 2° KIE value (kH/kD = 0.86 ± 0.08) measured for the Pro-d7 substrate indicates rehybridization of the prolyl nitrogen from sp(2) to sp(3) during the rate-limiting step of isomerization. No solvent kinetic isotope was measured by NMR exchange spectroscopy (kH2O/kD2O = 0.92 ± 0.12), indicating little or no involvement of exchangeable protons in the mechanism. These results support the formation of a simple twisted amide transition state as the mechanism for peptidyl prolyl isomerization catalyzed by Pin1. A model of the reaction mechanism is presented using crystal structures of Pin1 with ground state analogues and an inhibitor that resembles a twisted amide transition state. PMID:24116866

  3. Kinetic modeling of nucleation experiments involving SO2 and OH: new insights into the underlying nucleation mechanisms

    Directory of Open Access Journals (Sweden)

    F. Yu

    2009-10-01

    Full Text Available Nucleation is an important source of atmospheric aerosols which have significant climatic and health implications. Despite intensive theoretical and field studies over the past decades, the dominant nucleation mechanism in the lower troposphere remains to be mysterious. Several recent laboratory studies on atmospheric nucleation may shed light on this important problem. However, the most interesting finding from those studies was based on the derived H2SO4 concentration whose accuracy has not yet been evaluated by any other means. Moreover, the threshold H2SO4 concentration needed to reach the same degree of nucleation reported by two separate nucleation studies varies by about one order of magnitude. In this study, we apply a recently updated kinetic nucleation model to study the nucleation phenomena observed in those recent experiments. We show that the H2SO4 concentration can be estimated with a higher level of accuracy with the kinetic model by constraining the simulated particle size distributions with observed ones. We find that the required H2SO4 concentrations to achieve the best agreement between modeling and measurements are a factor of ~2 to 4 higher than reported in those experiments. More importantly, by comparing the derived thermodynamic properties associated with the nucleation process, we conclude that different unknown species may participate in the two separate nucleation experimental studies, which may explain the large difference in the reported threshold H2SO4 concentration. Although the unknown species involved has yet to be identified, the derived values of thermodynamic properties can serve as a valuable guideline for the search of their chemical identities using advanced quantum-chemical approaches.

  4. Kinetic modeling of nucleation experiments involving SO2 and OH: new insights into the underlying nucleation mechanisms

    Directory of Open Access Journals (Sweden)

    F. Yu

    2009-01-01

    Full Text Available Nucleation is an important source of atmospheric aerosols which have significant climatic and health implications. Despite intensive theoretical and field studies during past decades, the dominant nucleation mechanism in the lower troposphere remains to be mysterious. Several recent laboratory studies on atmospheric nucleation may shed light on this important problem. However, the most interesting finding from those studies was based on the H2SO4 concentration whose accuracy has not yet been evaluated by any other methods. Moreover, the threshold H2SO4 concentration needed to reach the same degree of nucleation reported by two separate nucleation studies varies by about one order of magnitude. In this study, we apply a recently updated kinetic nucleation model to study the nucleation phenomena observed in those recent experiments. We show that the H2SO4 concentration can be estimated with a higher level of accuracy with the kinetic model by constraining the simulated particle size distributions with observed ones. We find that the H2SO4 concentration was underestimated in those studies by a factor of ~2 to 4. More importantly, by comparing the derived thermodynamic properties associated with the nucleation process, we conclude that different unknown species may participate in the two separate nucleation experimental studies, which may explain the large difference in the reported threshold H2SO4 concentration. Although the unknown species involved has yet to be identified, the derived values of thermodynamic properties can serve as a valuable guideline for the search of their chemical identities using advanced quantum-chemical approaches.

  5. Analysis of the kinetic mechanism of recombinant human isoprenylcysteine carboxylmethyltransferase (Icmt

    Directory of Open Access Journals (Sweden)

    Baron Rudi A

    2004-12-01

    Full Text Available Abstract Background Isoprenylcysteine carboxyl methyltransferase (Icmt is the third of three enzymes that posttranslationally modify proteins that contain C-terminal CaaX motifs. The processing of CaaX proteins through this so-called prenylation pathway via a route initiated by addition of an isoprenoid lipid is required for both membrane targeting and function of the proteins. The involvement of many CaaX proteins such as Ras GTPases in oncogenesis and other aberrant proliferative disorders has led to the targeting of the enzymes involved in their processing for therapeutic development, necessitating a detailed understanding of the mechanisms of the enzymes. Results In this study, we have investigated the kinetic mechanism of recombinant human Icmt. In the reaction catalyzed by Icmt, S-adenosyl-L-methionine (AdoMet provides the methyl group that is transferred to the second substrate, the C-terminal isoprenylated cysteine residue of a CaaX protein, thereby generating a C-terminal prenylcysteine methyl ester on the protein. To facilitate the kinetic analysis of Icmt, we synthesized a new small molecule substrate of the enzyme, biotin-S-farnesyl-L-cysteine (BFC. Initial kinetic analysis of Icmt suggested a sequential mechanism for the enzyme that was further analyzed using a dead end competitive inhibitor, S-farnesylthioacetic acid (FTA. Inhibition by FTA was competitive with respect to BFC and uncompetitive with respect to AdoMet, indicating an ordered mechanism with SAM binding first. To investigate the order of product dissociation, product inhibition studies were undertaken with S-adenosyl-L-homocysteine (AdoHcy and the N-acetyl-S-farnesyl-L-cysteine methylester (AFCME. This analysis indicated that AdoHcy is a competitive inhibitor with respect to AdoMet, while AFCME shows a noncompetitive inhibition with respect to BFC and a mixed-type inhibition with respect to AdoMet. These studies established that AdoHcy is the final product released, and

  6. Computational thermal, chemical, fluid, and solid mechanics for geosystems management.

    Energy Technology Data Exchange (ETDEWEB)

    Davison, Scott; Alger, Nicholas; Turner, Daniel Zack; Subia, Samuel Ramirez; Carnes, Brian; Martinez, Mario J.; Notz, Patrick K.; Klise, Katherine A.; Stone, Charles Michael; Field, Richard V., Jr.; Newell, Pania; Jove-Colon, Carlos F.; Red-Horse, John Robert; Bishop, Joseph E.; Dewers, Thomas A.; Hopkins, Polly L.; Mesh, Mikhail; Bean, James E.; Moffat, Harry K.; Yoon, Hongkyu

    2011-09-01

    This document summarizes research performed under the SNL LDRD entitled - Computational Mechanics for Geosystems Management to Support the Energy and Natural Resources Mission. The main accomplishment was development of a foundational SNL capability for computational thermal, chemical, fluid, and solid mechanics analysis of geosystems. The code was developed within the SNL Sierra software system. This report summarizes the capabilities of the simulation code and the supporting research and development conducted under this LDRD. The main goal of this project was the development of a foundational capability for coupled thermal, hydrological, mechanical, chemical (THMC) simulation of heterogeneous geosystems utilizing massively parallel processing. To solve these complex issues, this project integrated research in numerical mathematics and algorithms for chemically reactive multiphase systems with computer science research in adaptive coupled solution control and framework architecture. This report summarizes and demonstrates the capabilities that were developed together with the supporting research underlying the models. Key accomplishments are: (1) General capability for modeling nonisothermal, multiphase, multicomponent flow in heterogeneous porous geologic materials; (2) General capability to model multiphase reactive transport of species in heterogeneous porous media; (3) Constitutive models for describing real, general geomaterials under multiphase conditions utilizing laboratory data; (4) General capability to couple nonisothermal reactive flow with geomechanics (THMC); (5) Phase behavior thermodynamics for the CO2-H2O-NaCl system. General implementation enables modeling of other fluid mixtures. Adaptive look-up tables enable thermodynamic capability to other simulators; (6) Capability for statistical modeling of heterogeneity in geologic materials; and (7) Simulator utilizes unstructured grids on parallel processing computers.

  7. Acceleration of the KINETICS Integrated Dynamical/Chemical Computational Model Using MPI

    Science.gov (United States)

    Grossman, Max; Willacy, Karen; Allen, Mark

    2011-01-01

    Understanding the evolution of a planet's atmosphere not only provides a better theoretical understanding of planetary physics and the formation of planets, but also grants useful insight into Earth's own atmosphere. One of the tools used at JPL for the modeling of planetary atmospheres and protostellar disks is KINETICS. KINETICS can simulate years of complex dynamics and chemistry.

  8. Combustion in Homogeneous Charge Compression Ignition Engines: Experiments and Detailed Chemical Kinetic Simulations

    Energy Technology Data Exchange (ETDEWEB)

    Flowers, D L

    2002-06-07

    Homogeneous charge compression ignition (HCCI) engines are being considered as an alternative to diesel engines. The HCCI concept involves premixing fuel and air prior to induction into the cylinder (as is done in current spark-ignition engine) then igniting the fuel-air mixture through the compression process (as is done in current diesel engines). The combustion occurring in an HCCI engine is fundamentally different from a spark-ignition or Diesel engine in that the heat release occurs as a global autoignition process, as opposed to the turbulent flame propagation or mixing controlled combustion used in current engines. The advantage of this global autoignition is that the temperatures within the cylinder are uniformly low, yielding very low emissions of oxides of nitrogen (NO{sub x}, the chief precursors to photochemical smog). The inherent features of HCCI combustion allows for design of engines with efficiency comparable to, or potentially higher than, diesel engines. While HCCI engines have great potential, several technical barriers exist which currently prevent widespread commercialization of this technology. The most significant challenge is that the combustion timing cannot be controlled by typical in-cylinder means. Means of controlling combustion have been demonstrated, but a robust control methodology that is applicable to the entire range of operation has yet to be developed. This research focuses on understanding basic characteristics of controlling and operating HCCI engines. Experiments and detailed chemical kinetic simulations have been applied to the characterize some of the fundamental operational and design characteristics of HCCI engines. Experiments have been conducted on single and multi-cylinder engines to investigate general features of how combustion timing affects the performance and emissions of HCCI engines. Single-zone modeling has been used to characterize and compare the implementation of different control strategies. Multi

  9. Mixed butanols addition to gasoline surrogates: Shock tube ignition delay time measurements and chemical kinetic modeling

    KAUST Repository

    AlRamadan, Abdullah S.

    2015-10-01

    The demand for fuels with high anti-knock quality has historically been rising, and will continue to increase with the development of downsized and turbocharged spark-ignition engines. Butanol isomers, such as 2-butanol and tert-butanol, have high octane ratings (RON of 105 and 107, respectively), and thus mixed butanols (68.8% by volume of 2-butanol and 31.2% by volume of tert-butanol) can be added to the conventional petroleum-derived gasoline fuels to improve octane performance. In the present work, the effect of mixed butanols addition to gasoline surrogates has been investigated in a high-pressure shock tube facility. The ignition delay times of mixed butanols stoichiometric mixtures were measured at 20 and 40bar over a temperature range of 800-1200K. Next, 10vol% and 20vol% of mixed butanols (MB) were blended with two different toluene/n-heptane/iso-octane (TPRF) fuel blends having octane ratings of RON 90/MON 81.7 and RON 84.6/MON 79.3. These MB/TPRF mixtures were investigated in the shock tube conditions similar to those mentioned above. A chemical kinetic model was developed to simulate the low- and high-temperature oxidation of mixed butanols and MB/TPRF blends. The proposed model is in good agreement with the experimental data with some deviations at low temperatures. The effect of mixed butanols addition to TPRFs is marginal when examining the ignition delay times at high temperatures. However, when extended to lower temperatures (T < 850K), the model shows that the mixed butanols addition to TPRFs causes the ignition delay times to increase and hence behaves like an octane booster at engine-like conditions. © 2015 The Combustion Institute.

  10. A computational methodology for formulating gasoline surrogate fuels with accurate physical and chemical kinetic properties

    KAUST Repository

    Ahmed, Ahfaz

    2015-03-01

    Gasoline is the most widely used fuel for light duty automobile transportation, but its molecular complexity makes it intractable to experimentally and computationally study the fundamental combustion properties. Therefore, surrogate fuels with a simpler molecular composition that represent real fuel behavior in one or more aspects are needed to enable repeatable experimental and computational combustion investigations. This study presents a novel computational methodology for formulating surrogates for FACE (fuels for advanced combustion engines) gasolines A and C by combining regression modeling with physical and chemical kinetics simulations. The computational methodology integrates simulation tools executed across different software platforms. Initially, the palette of surrogate species and carbon types for the target fuels were determined from a detailed hydrocarbon analysis (DHA). A regression algorithm implemented in MATLAB was linked to REFPROP for simulation of distillation curves and calculation of physical properties of surrogate compositions. The MATLAB code generates a surrogate composition at each iteration, which is then used to automatically generate CHEMKIN input files that are submitted to homogeneous batch reactor simulations for prediction of research octane number (RON). The regression algorithm determines the optimal surrogate composition to match the fuel properties of FACE A and C gasoline, specifically hydrogen/carbon (H/C) ratio, density, distillation characteristics, carbon types, and RON. The optimal surrogate fuel compositions obtained using the present computational approach was compared to the real fuel properties, as well as with surrogate compositions available in the literature. Experiments were conducted within a Cooperative Fuels Research (CFR) engine operating under controlled autoignition (CAI) mode to compare the formulated surrogates against the real fuels. Carbon monoxide measurements indicated that the proposed surrogates

  11. Mechanism of radiation-chemical and pyrolytic transformations in lexan

    OpenAIRE

    Roustam Aliev; Rafael Navarro-González

    2006-01-01

    We report here a new approach to study the mechanism of radiation-chemical transformations in polymeric materials based on the combined analysis of radiolytic gases, and pyrolytic products from preirradiated polymers by flash pyrolysis coupled to gas chromatography –Fourier transformed infrared spectroscopy– mass spectrometry with electron impact mode (GC-FTIR-MS). Lexan® (bisphenol-A polycarbonate) was studied in the dose range from 0.125 to 1.0 MGy. Lexan irradiation was accompanied by the ...

  12. Defect centers in chemical-mechanical polished MOS oxides

    Energy Technology Data Exchange (ETDEWEB)

    Shaneyfelt, M.R.; Warren, W.L.; Hetherington, D.L.; Timon, R.P.; Resnick, P.J.; Winokur, P.S.

    1994-12-31

    Defect centers generated in vacuum-ultraviolet irradiated chemical-mechanical polished oxides have been characterized using electron paramagnetic resonance and C-V analysis. Both oxide trap E{sub {gamma}} and interface trap P{sub b0} centers were detected in unpolished and polished oxides. In addition, another interface defect center known as the P{sub b1} center was only identified in the polished oxides, suggesting that the polishing process altered the SiO{sub 2}/Si interface.

  13. Kinetics and Mechanism of Ruthenium(III) Catalyzed Oxidation of Butanone and Uncatalyzed Oxidation of Cychlohexanone by Cerium(IV) in Acid Sulphate Medium

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Priyamvada; Hemkar, Shalini; Khandelwal, C. L.; Sharma, P. D. [Univ. of Rajasthan, Jaipur (India)

    2012-02-15

    The kinetics of ruthenium(III) chloride catalyzed oxidation of butanone and uncatalyzed oxidation of cyclohexanone by cerium(IV) in sulphuric acid medium have been studied. The kinetic rate law(I) in case of butanone conforms to the proposed mechanism. Kinetics and activation parameters have been evaluated conventionally. Kinetically preferred mode of reaction is via ketonic and not the enolic forms.

  14. Is case-based learning an effective teaching strategy to challenge students' alternative conceptions regarding chemical kinetics?

    Science.gov (United States)

    Yalçınkaya, Eylem; Taştan-Kırık, Özgecan; Boz, Yezdan; Yıldıran, Demet

    2012-07-01

    Background: Case-based learning (CBL) is simply teaching the concept to the students based on the cases. CBL involves a case, which is a scenario based on daily life, and study questions related to the case, which allows students to discuss their ideas. Chemical kinetics is one of the most difficult concepts for students in chemistry. Students have generally low levels of conceptual understanding and many alternative conceptions regarding it. Purpose: This study aimed to explore the effect of CBL on dealing with students' alternative conceptions about chemical kinetics. Sample: The sample consists of 53 high school students from one public high school in Turkey. Design and methods : Nonequivalent pre-test and post-test control group design was used. Reaction Rate Concept Test and semi-structured interviews were used for data collection. Convenience sampling technique was followed. For data analysis, the independent samples t-test and ANOVA was performed. Results : Both concept test and interview results showed that students instructed with cases had better understanding of core concepts of chemical kinetics and had less alternative conceptions related to the subject matter compared to the control group students, despite the fact that it was impossible to challenge all the alternative conceptions in the experimental group. Conclusions: CBL is an effective teaching method for challenging students' alternative conceptions in the context of chemical kinetics. Since using cases in small groups and whole class discussions has been found to be an effective way to cope with the alternative conceptions, it can be applied to other subjects and grade levels in high schools with a higher sample size. Furthermore, the effect of this method on academic achievement, motivation and critical thinking skills are other variables that can be investigated for future studies in the subject area of chemistry.

  15. Research on the molecular scale material removal mechanism in chemical mechanical polishing

    Institute of Scientific and Technical Information of China (English)

    WANG YongGuang; ZHAO YongWu

    2008-01-01

    This paper investigates a novel molecular scale material removal mechanism in chemical mechanical polishing (CMP) by incorporating the order-of-magnitude calculations,particle adhesion force,defect of wafer,thickness of newly formed oxidizedlayer,and large deformation of pad/particle not discussed by previous analysis.The theoretical analysis and experimental data show that the indentation depth,scratching depth and polishing surface roughness are on the order of molecular scale or less.There.fore,this novel mechanism has gained the support from wide order-of- magnitude calculations and experimental data.In addition,with the decrease in the particle size,the molecular scale removal mechanism is plausibly one of the most promising removal mechanisms to clarify the CMP polishing process.The results are useful to substantiating the molecular-scale mechanism of the CMP material removal in addition to its underlying theoretical foundation.

  16. Development of a hybrid chemical/mechanical heat pump

    Science.gov (United States)

    Grzyll, Lawrence R.; Silvestri, John J.; Scaringe, Robert P.

    1991-01-01

    The authors present the current development status of a hybrid chemical/mechanical heat pump for low-lift applications. The heat pump provides electronics cooling by evaporating a pure refrigerant from an absorbent/refrigerant mixture in a generator/cold plate. The current development focused on evaluation of absorbent/refrigerant pairs, corrosion testing, pump and compressor design, and electronic cold plate design. Two cycle configurations were considered. The first configuration utilized a standard mechanical compressor and pump. The second cycle configuration investigated pumps and compressors with non-moving parts. An innovative generator/cold plate design is also presented. The development to date shows that this cycle has about the same performance as standard vapor compression heat pumps with standard refrigerants but may have some performance and reliability advantages over vapor compression heat pumps.

  17. Kinetics and Mechanisms of γ′ Reprecipitation in a Ni-based Superalloy

    Science.gov (United States)

    Masoumi, F.; Shahriari, D.; Jahazi, M.; Cormier, J.; Devaux, A.

    2016-01-01

    The reprecipitation mechanisms and kinetics of γ′ particles during cooling from supersolvus and subsolvus temperatures were studied in AD730TM Ni-based superalloy using Differential Thermal Analysis (DTA). The evolution in the morphology and distribution of reprecipitated γ′ particles was investigated using Field Emission Gun Scanning Electron Microscopy (FEG-SEM). Depending on the cooling rate, γ′ particles showed multi or monomodal distribution. The irregularity growth characteristics observed at lower cooling rates were analyzed in the context of Mullins and Sekerka theory, and allowed the determination of a critical size of γ′ particles above which morphological instability appears. Precipitation kinetics parameters were determined using a non-isothermal JMA model and DTA data. The Avrami exponent was determined to be in the 1.5–2.3 range, suggesting spherical or irregular growth. A methodology was developed to take into account the temperature dependence of the rate coefficient k(T) in the non-isothermal JMA equation. In that regard, a function for k(T) was developed. Based on the results obtained, reprecipitation kinetics models for low and high cooling rates are proposed to quantify and predict the volume fraction of reprecipitated γ′ particles during the cooling process. PMID:27338868

  18. Kinetics and Mechanisms of γ' Reprecipitation in a Ni-based Superalloy.

    Science.gov (United States)

    Masoumi, F; Shahriari, D; Jahazi, M; Cormier, J; Devaux, A

    2016-01-01

    The reprecipitation mechanisms and kinetics of γ' particles during cooling from supersolvus and subsolvus temperatures were studied in AD730(TM) Ni-based superalloy using Differential Thermal Analysis (DTA). The evolution in the morphology and distribution of reprecipitated γ' particles was investigated using Field Emission Gun Scanning Electron Microscopy (FEG-SEM). Depending on the cooling rate, γ' particles showed multi or monomodal distribution. The irregularity growth characteristics observed at lower cooling rates were analyzed in the context of Mullins and Sekerka theory, and allowed the determination of a critical size of γ' particles above which morphological instability appears. Precipitation kinetics parameters were determined using a non-isothermal JMA model and DTA data. The Avrami exponent was determined to be in the 1.5-2.3 range, suggesting spherical or irregular growth. A methodology was developed to take into account the temperature dependence of the rate coefficient k(T) in the non-isothermal JMA equation. In that regard, a function for k(T) was developed. Based on the results obtained, reprecipitation kinetics models for low and high cooling rates are proposed to quantify and predict the volume fraction of reprecipitated γ' particles during the cooling process. PMID:27338868

  19. Kinetics and mechanism of thermal degradation of pentose- and hexose-based carbohydrate polymers.

    Science.gov (United States)

    Akbar, Jamshed; Iqbal, Mohammad S; Massey, Shazma; Masih, Rashid

    2012-10-15

    This work aims at study of thermal degradation kinetics and mechanism of pentose- and hexose-based carbohydrate polymers isolated from Plantago ovata (PO), Salvia aegyptiaca (SA) and Ocimum basilicum (OB). The analysis was performed by isoconversional method. The materials exhibited mainly two-stage degradation. The weight loss at ambient-115°C characterized by low activation energy corresponds to loss of moisture. The kinetic triplets consisting of E, A and g(α) model of the materials were determined. The major degradation stage represents a loss of high boiling volatile components. This stage is exothermic in nature. Above 340°C complete degradation takes place leaving a residue of 10-15%. The master plots of g(α) function clearly differentiated the degradation mechanism of hexose-based OB and SA polymers and pentose-based PO polymer. The pentose-based carbohydrate polymer showed D(4) type and the hexose-based polymers showed A(4) type degradation mechanism. PMID:22939355

  20. DNA-Binding Kinetics Determines the Mechanism of Noise-Induced Switching in Gene Networks.

    Science.gov (United States)

    Tse, Margaret J; Chu, Brian K; Roy, Mahua; Read, Elizabeth L

    2015-10-20

    Gene regulatory networks are multistable dynamical systems in which attractor states represent cell phenotypes. Spontaneous, noise-induced transitions between these states are thought to underlie critical cellular processes, including cell developmental fate decisions, phenotypic plasticity in fluctuating environments, and carcinogenesis. As such, there is increasing interest in the development of theoretical and computational approaches that can shed light on the dynamics of these stochastic state transitions in multistable gene networks. We applied a numerical rare-event sampling algorithm to study transition paths of spontaneous noise-induced switching for a ubiquitous gene regulatory network motif, the bistable toggle switch, in which two mutually repressive genes compete for dominant expression. We find that the method can efficiently uncover detailed switching mechanisms that involve fluctuations both in occupancies of DNA regulatory sites and copy numbers of protein products. In addition, we show that the rate parameters governing binding and unbinding of regulatory proteins to DNA strongly influence the switching mechanism. In a regime of slow DNA-binding/unbinding kinetics, spontaneous switching occurs relatively frequently and is driven primarily by fluctuations in DNA-site occupancies. In contrast, in a regime of fast DNA-binding/unbinding kinetics, switching occurs rarely and is driven by fluctuations in levels of expressed protein. Our results demonstrate how spontaneous cell phenotype transitions involve collective behavior of both regulatory proteins and DNA. Computational approaches capable of simulating dynamics over many system variables are thus well suited to exploring dynamic mechanisms in gene networks.

  1. Kinetics and Modeling of Chemical Leaching of Sphalerite Concentrate Using Ferric Iron in a Redox-controlled Reactor

    Institute of Scientific and Technical Information of China (English)

    宋健; 高玲; 林建群; 吴洪斌; 林建强

    2013-01-01

    This work presents a study for chemical leaching of sphalerite concentrate under various constant Fe3+concentrations and redox potential conditions. The effects of Fe3+ concentration and redox potential on chemical leaching of sphalerite were investigated. The shrinking core model was applied to analyze the experimental results. It was found that both the Fe3+ concentration and the redox potential controlled the chemical leaching rate of sphalerite. A new kinetic model was developed, in which the chemical leaching rate of sphalerite was proportional to Fe3+concentration and Fe3+/Fe2+ratio. All the model parameters were evaluated from the experimental data. The model predictions fit well with the experimental observed values.

  2. Kinetics and Mechanism of Oxidation of Ethylene Glycol Monoethylether by Diperiodatonickelate(IV) in Alkaline Medium

    Institute of Scientific and Technical Information of China (English)

    单金缓; 魏海英; 申世刚; 孙汉文

    2003-01-01

    The kinetics of oxidation of ethylene glycol monoethylether (EGE) by diperiodatonickelate(IV) ion (DPN) was studied by spectrophotometry in alkaline medium. The reaction rate showed first order dependence on Ni(IV) and positive fractional order with respect to EGE. The pseudo-first order rate conslants, kobs increased with the increase of [OH-] and decreased with the increase of [IO4- ]. Added salts had little effect on the rate and no free radical was detected. Based on these,the mechanism including the equilibrium between DPN and EGE was proposed. Furthermore, the activation parameters of the reaction were calculated.

  3. Andrographolide sodium bisulphite-induced inactivation of urease: inhibitory potency, kinetics and mechanism

    OpenAIRE

    Mo, Zhi-Zhun; Wang, Xiu-Fen; Zhang, Xie; Su, Ji-Yan; Chen, Hai-Ming; Liu, Yu-Hong; Zhang, Zhen-biao; Xie, Jian-Hui; Su, Zi-Ren

    2015-01-01

    Background The inhibitory effect of andrographolide sodium bisulphite (ASB) on jack bean urease (JBU) and Helicobacter pylori urease (HPU) was performed to elucidate the inhibitory potency, kinetics and mechanism of inhibition in 20 mM phosphate buffer, pH 7.0, 2 mM EDTA, 25 °C. Methods The ammonia formations, indicator of urease activity, were examined using modified spectrophotometric Berthelot (phenol-hypochlorite) method. The inhibitory effect of ASB was characterized with IC50 values. Li...

  4. Kinetics and Mechanism of Oxidation of Some Diols by Dihydroxydiperiodatoargentate(Ⅲ) in Alkaline Medium

    Institute of Scientific and Technical Information of China (English)

    SHAN, Jin-Huan; LI, Sheng-Min; HUO, Shu-Ying; SHEN, Shi-Gang; SUN, Han-Wen

    2006-01-01

    The kinetics of oxidation of ethylene glycol and 1,3-butylene glycol by dihydroxydiperiodatoargentate(Ⅲ) in alkaline medium have been studied by spectrophotometry in the range of 298.2-318.2 K. It is shown that the reaction was first order with respect to each reductant and Ag(Ⅲ), and kobs increased with an increase of [OH-]. A plausible mechanism of reaction involving a pre-equilibrium of adduct formation between complex and reductants was proposed, which could be applied to explain all experimental phenomena, and the activation parameters of the ratedetermining step have been also calculated.

  5. Nanostructure formation and its effects on the mechanical properties of kinetic sprayed titanium coating

    International Nuclear Information System (INIS)

    Research highlights: The reports of the deformation microstructures at the microscopic level of kinetic sprayed commercially pure titanium coatings are currently lacking in the literature, although some macroscopic aspects of bonding, deposition characteristics, and mechanical behaviors of the coatings have already been reported. The formation of considerably homogeneous and randomly orientated equiaxed nanograins with some dislocation-free nanograins (250 nm) and smaller dislocation-free grains with non-equilibrium grain boundaries (<100 nm) was determined to be associated with both the strain hardening and the ductile dimple fracture of the coating.

  6. Effect of mechanical stress on the kinetics of heterogeneous electron transfer.

    Science.gov (United States)

    Sun, Peng; Liu, Zhen; Yu, Honghui; Mirkin, Michael V

    2008-09-16

    The scanning electrochemical microscope (SECM) combined with a computerized tensile stage was employed to measure the kinetics of electron transfer (ET) reactions at stainless steel electrodes as a function of the applied mechanical stress. Reproducible current versus distance curves were obtained for different values of the tensile stress applied to a stainless steel (T-316) sample by using hexaammineruthenium as a redox mediator. The dependences of the extracted rate constant on substrate potential (i.e., Tafel plots, ln k versus E) were linear, in agreement with classical electrochemical theory. Possible origins of the stress effect on the ET rate and its implications for studies of stress corrosion cracking are discussed. PMID:18715024

  7. Kinetics and mechanism of oxidation of acetanilide by quinquevalent vanadium in acid medium

    International Nuclear Information System (INIS)

    The kinetics of the oxidation of acetanilide with vanadium(V) in sulphuric acid medium at constant ionic strength has been studied. The reaction is first order with oxidant. The order of reaction in acetanilide varies from one to zero. The reaction follows an acid catalyzed independent path, exhibiting square dependence in H+. A Bunnett plot indicates that the water acts as a nucleophile. The thermodynamic parameters have been computed. A probable reaction mechanism and rate law consistent with these data are given. (Author)

  8. Kinetic Mechanism of OMP Synthase:  A Slow Physical Step Following

    DEFF Research Database (Denmark)

    Wang, G.P.; Lundegaard, Claus; Jensen, Kaj Frank;

    1999-01-01

    , a burst (nrev = 0.7/dimer; k = 300 s-1) was also noted. These results allowed us to develop a complete kinetic mechanism for OPRTase, in which a rapid phosphoribosyl transfer reaction at equilibrium is followed by a slow step involving release of product. When the microviscosity, ¿rel, of the reaction......, solvent-exposed loop descends during catalysis to shield the active site. In the accompanying paper, the slow product release step is shown to relate to movement of the solvent-exposed loop....

  9. Kinetics and reaction mechanism of hydroxyl radical reaction with methyl formate

    Energy Technology Data Exchange (ETDEWEB)

    Good, D.A.; Hanson, J.; Francisco, J.S.; Li, Z.; Jeong, G.R.

    1999-12-16

    Ab initio molecular orbital theory has been used to examine the kinetics and mechanism for the reaction of hydroxyl radical with methyl formate. From the ab initio parameters the room temperature rate constant is calculated and found to be in good agreement with the experimental determination. It is found that 86% of the reaction proceeds via abstraction of the carbonyl hydrogen from methyl formate by hydroxyl radical, resulting in the formation of CH{sub 3}OCO radical. CH{sub 3}OCO is expected to oxidize to formaldehyde and carbon dioxide under tropospheric conditions.

  10. A binomial stochastic kinetic approach to the Michaelis-Menten mechanism

    Science.gov (United States)

    Lente, Gábor

    2013-05-01

    This Letter presents a new method that gives an analytical approximation of the exact solution of the stochastic Michaelis-Menten mechanism without computationally demanding matrix operations. The method is based on solving the deterministic rate equations and then using the results as guiding variables of calculating probability values using binomial distributions. This principle can be generalized to a number of different kinetic schemes and is expected to be very useful in the evaluation of measurements focusing on the catalytic activity of one or a few individual enzyme molecules.

  11. Two micro-mechanical techniques for studying the enzymatic maceration kinetics of apple parenchyma

    OpenAIRE

    Maingonnat, J.F.; Missang, C.E.; Baron, A; Renard, C.M.G.C.

    2014-01-01

    The enzymatic texture loss during apple maceration was studied by two micro-mechanical techniques. The first technique consisted of a 5% strain compression cycles at a strain rate of 4.5 x 10 4 s -1. The second technique consisted on micro-puncture of the apple parenchyma with a small needle. The first technique led to the peripheral tissues degradation modelling with a first order kinetic reaction or a more pertinent Weibull function. The second technique evidenced that the jagged part of t...

  12. Simple Numerical Method for Kinetical Investigation of Planar Mechanical Systems with Two Degrees of Freedom

    Directory of Open Access Journals (Sweden)

    István Bíró

    2016-01-01

    Full Text Available The aim of this article is to demonstrate the application of a simple numerical method which is suitable for motion analysis of different mechanical systems. For mechanical engineer students it is important task. Mechanical systems consisting of rigid bodies are linked to each other by different constraints. Kinematical and kinetical analysis of them leads to integration of second order differential equations. In this way the kinematical functions of parts of mechanical systems can be determined. Degrees of freedom of the mechanical system increase as a result of built-in elastic parts. Numerical methods can be applied to solve such problems. The simple numerical method will be demonstrated in MS Excel by author by the aid of two examples. MS Excel is a quite useful tool for mechanical engineers because easy to use it and details can be seen moreover failures can be noticed. Some parts of results obtained by using the numerical method were checked by analytical way. The published method can be used in higher education for mechanical engineer students.

  13. Influence of oxygen on the chemical stage of radiobiological mechanism

    Science.gov (United States)

    Barilla, Jiří; Lokajíček, Miloš V.; Pisaková, Hana; Simr, Pavel

    2016-07-01

    The simulation of the chemical stage of radiobiological mechanism may be very helpful in studying the radiobiological effect of ionizing radiation when the water radical clusters formed by the densely ionizing ends of primary or secondary charged particle may form DSBs damaging DNA molecules in living cells. It is possible to study not only the efficiency of individual radicals but also the influence of other species or radiomodifiers (mainly oxygen) being present in water medium during irradiation. The mathematical model based on Continuous Petri nets (proposed by us recently) will be described. It makes it possible to analyze two main processes running at the same time: chemical radical reactions and the diffusion of radical clusters formed during energy transfer. One may study the time change of radical concentrations due to the chemical reactions running during diffusion process. Some orientation results concerning the efficiency of individual radicals in DSB formation (in the case of Co60 radiation) will be presented; the influence of oxygen present in water medium during irradiation will be shown, too.

  14. Chemical and mechanical weed control in soybean (Glycine max

    Directory of Open Access Journals (Sweden)

    Weber, Jonas Felix

    2016-02-01

    Full Text Available In this study we investigated the possibility of chemical and mechanical weed control strategies in soybean. Soybean field experiments were carried out in 2013 and 2014 in Southern Germany. Five treatments including common herbicide mixtures and four mechanical weed control treatments, implementing a harrow and a hoe, were tested at different locations. In the herbicide experiments two treatments were applied by PRE emergence herbicides (metribuzin, clomazone, dimethenamid and metribuzin, flufenacet, clomazone and another two treatments were sprayed with a combination of PRE + POST emergence herbicides (metribuzin, flufenacet, thifensulfuron and pendimethalin, thifensulfuron, bentazone, cycloxydim. Furthermore, a POST herbicide treatment was implemented (thifensulfuron, bentazone, thifensulfuron and fluazifop-P-butyl. In the mechanical weed control experiments, treatments were: three times hoeing, PRE emergence harrowing plus three times hoeing, hoeing and harrowing in rotation or three times harrowing. In both experiments an untreated control was included. A 90% weed control efficacy and 23% yield increase was observed in the POST herbicide treatment. PRE + POST treatments resulted in 92% to 99% weed control efficiency and 15% yield increase compared to the untreated control. In the mechanical weed control experiments the combination of PRE emergence harrowing and POST emergence hoeing resulted in 82% weed control efficiency and 34% higher yield compared to the untreated control. Less weed control efficiency (72% was observed in the harrow treatment, leading to 20% higher yield compared to the control. The suitability of both strategies for implementation in “Integrated Weed Management” has been investigated.

  15. Three-stage autoignition of gasoline in an HCCI engine: An experimental and chemical kinetic modeling investigation

    Energy Technology Data Exchange (ETDEWEB)

    Machrafi, Hatim; Cavadias, Simeon [UPMC Universite Paris 06, LGPPTS, Ecole Nationale Superieure de Chimie de Paris (France); UPMC Universite Paris 06, Institut Jean Le Rond D' Alembert (France)

    2008-12-15

    The alternative HCCI combustion mode presents a possible means for decreasing the pollution with respect to conventional gasoline or diesel engines, while maintaining the efficiency of a diesel engine or even increasing it. This paper investigates the possibility of using gasoline in an HCCI engine and analyzes the autoignition of gasoline in such an engine. The compression ratio that has been used is 13.5, keeping the inlet temperature at 70 C, varying the equivalence ratio from 0.3 to 0.54, and the EGR (represented by N{sub 2}) ratio from 0 to 37 vol%. For comparison, a PRF95 and a surrogate containing 11 vol% n-heptane, 59 vol% iso-octane, and 30 vol% toluene are used. A previously validated kinetic surrogate mechanism is used to analyze the experiments and to yield possible explanations to kinetic phenomena. From this work, it seems quite possible to use the high octane-rated gasoline for autoignition purposes, even under lean inlet conditions. Furthermore, it appeared that gasoline and its surrogate, unlike PRF95, show a three-stage autoignition. Since the PRF95 does not contain toluene, it is suggested by the kinetic mechanism that the benzyl radical, issued from toluene, causes this so-defined ''obstructed preignition'' and delaying thereby the final ignition for gasoline and its surrogate. The results of the kinetic mechanism supporting this explanation are shown in this paper. (author)

  16. Mechanical and chemical behavior of intergranular fluids in nonhydrostatically stressed rocks at low temperature

    Institute of Scientific and Technical Information of China (English)

    刘亮明; 彭省临

    2001-01-01

    Intergranular fluids within the nonhydrostatically stressed solids are a sort of important fluids in the crust. Research on the mechanical and chemical behavior of the intergranular fluids in nonhydrostatically stressed rocks at low temperature is a key for understanding deformation and syntectonic geochemical processes in mid to shallow crust. Theoretically, it is suggested that the fluid film sandwiched between solid grains is one of the main states of intergranular fluids in the nonhydrostatically stressed solids. Their superthin thickness makes the fluid films have the mechanical and chemical behavior very different from the common fluids. Because of hydration force, double-layer repulsive force or osmotic pressure due to double-layer, the fluid films can transmit nonhydrostatic stress. The solid minerals-intergranular fluids interaction and mass transfer by intergranular fluids is stress-related, because the stress in solid minerals can enhance the free energy of solid matter on the interfaces. The thermodynamic and kinetic equations for the simple case of stress induced processes are derived.

  17. Biofilm Formation Mechanisms of Pseudomonas aeruginosa Predicted via Genome-Scale Kinetic Models of Bacterial Metabolism.

    Science.gov (United States)

    Vital-Lopez, Francisco G; Reifman, Jaques; Wallqvist, Anders

    2015-10-01

    A hallmark of Pseudomonas aeruginosa is its ability to establish biofilm-based infections that are difficult to eradicate. Biofilms are less susceptible to host inflammatory and immune responses and have higher antibiotic tolerance than free-living planktonic cells. Developing treatments against biofilms requires an understanding of bacterial biofilm-specific physiological traits. Research efforts have started to elucidate the intricate mechanisms underlying biofilm development. However, many aspects of these mechanisms are still poorly understood. Here, we addressed questions regarding biofilm metabolism using a genome-scale kinetic model of the P. aeruginosa metabolic network and gene expression profiles. Specifically, we computed metabolite concentration differences between known mutants with altered biofilm formation and the wild-type strain to predict drug targets against P. aeruginosa biofilms. We also simulated the altered metabolism driven by gene expression changes between biofilm and stationary growth-phase planktonic cultures. Our analysis suggests that the synthesis of important biofilm-related molecules, such as the quorum-sensing molecule Pseudomonas quinolone signal and the exopolysaccharide Psl, is regulated not only through the expression of genes in their own synthesis pathway, but also through the biofilm-specific expression of genes in pathways competing for precursors to these molecules. Finally, we investigated why mutants defective in anthranilate degradation have an impaired ability to form biofilms. Alternative to a previous hypothesis that this biofilm reduction is caused by a decrease in energy production, we proposed that the dysregulation of the synthesis of secondary metabolites derived from anthranilate and chorismate is what impaired the biofilms of these mutants. Notably, these insights generated through our kinetic model-based approach are not accessible from previous constraint-based model analyses of P. aeruginosa biofilm

  18. Ozonolysis of alpha-pinene and beta-pinene: kinetics and mechanism.

    Science.gov (United States)

    Zhang, Dan; Zhang, Renyi

    2005-03-15

    A combined quantum-chemical and RRKM/ME (ME--master equation) approach is employed to investigate the structures, energetics, and kinetics of intermediate and stable species, and the yields of stabilized carbonyl oxides and OH radicals from the alpha-pinene and beta-pinene ozonolysis reactions. The cycloaddition of O(3) is highly exothermic, with the reaction energies of 55.1 and 51.1 kcal mol(-1) for alpha- and beta-pinenes, respectively. Cleavage of primary ozonides yields carbonyl oxides with the barrier height of 12.2-17.5 kcal mol(-1). For the prompt reactions of carbonyl oxides from alpha- and beta-pinene ozonolysis, H migration to hydroperoxides represents the dominant pathway over ring closure to dioxiranes. The kinetic calculations indicate a significant portion of stabilization for alpha- and beta-carbonyl oxides. The yields of stabilized carbonyl oxides are estimated to be 0.34 for alpha-pinene and 0.22 for beta-pinene. The applicability of theoretical methods for investigation of oxidation reactions of large hydrocarbon molecules is demonstrated.

  19. Adsorption/desorption of Direct Yellow 28 on apatitic phosphate: Mechanism, kinetic and thermodynamic studies

    Directory of Open Access Journals (Sweden)

    H. El Boujaady

    2014-10-01

    Full Text Available In this study, the adsorption potential of apatitic tricalcium phosphate for the removal of Direct Yellow 28 (DY28 from aqueous solution has been investigated by using batch mode experiments. The effects of different parameters such as pH, adsorbent dosage, initial dye concentration, contact time, addition of ions and temperature have been studied to understand the adsorption behavior of the adsorbent under various conditions. The adsorbent has been characterized by pHzpc measurement, chemical analyses, FTIR, XRD and TEM. The Langmuir and Freundlich models are found to be the best to describe the equilibrium isotherm data, with a maximum monolayer adsorption capacity of 67.02 mg g−1. Thermodynamic parameters including the Gibbs free energy ΔG, enthalpy ΔH, and entropy ΔS have revealed that the adsorption of DY28 on the apatitic tricalcium phosphate is feasible, spontaneous and endothermic. Among the kinetic models tested for apatitic tricalcium phosphate, the pseudo-second-order model fits the kinetic data well. The introduction of orthophosphate ions in the medium causes a decrease of adsorption. The addition of Ca2+ ions favors the adsorption. The results of this study have demonstrated the effectiveness and feasibility of the apatitic tricalcium phosphate for the removal of DY28 from aqueous solution.

  20. Curing kinetics, mechanism and chemorheological behavior of methanol etherified amino/novolac epoxy systems

    Directory of Open Access Journals (Sweden)

    S. F. Zhao

    2014-02-01

    Full Text Available The curing kinetics and mechanism of epoxy novolac resin (DEN and modified epoxy novolac resin (MDEN with methanol etherified amino resin were studied by means of differential scanning calorimetry (DSC, Fourier transforminfrared (FT-IR spectroscopy and chemorheological analysis. Their kinetics parameters and models of the curing were examined utilizing isoconversional methods, Flynn-Wall-Ozawa and Friedman methods. For the DEN mixture, its average activation energy (Ea was 71.05 kJ/mol and the autocatalytic model was established to describe the curing reaction. The MDEN mixture exhibited three dominant curing processes, termed as reaction 1, reaction 2 and reaction 3; and their Ea were 70.05, 106.55 and 101.91 kJ/mol, respectively. Besides, Ea of reaction 1 was similar to that of DEN mixture, while Ea of reactions 2 and 3 corresponded to that of the etherification reaction between hydroxyl and epoxide group. Moreover, these three dominant reactions were nth order in nature. Furthermore, their curing mechanisms were proposed from the results of DSC and FTIR. The chemorheological behavior was also investigated to obtain better plastics products via optimizing the processing schedules.

  1. Lagging and Its Kinetic Mechanism of Hydrocarbon Re-generation from Organic Matters in Coals

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Based on the composite analysis of the coal sample series with natural and artificial maturation, the lagging and its kinetic mechanism of the hydrocarbon re-generation from the organic matters in coals were studied using the Rock-Eval gas chromatogram (Py-GC) method. The results show that the maturation at the hydrocarbon re-generation peak shifts regularly forward with increasing the starting maturation and the deadline of the hydrocarbon re-generation lies about at 4. 0% Ro. The difference value between the peak and starting maturation of the hydrocarbon regeneration develops in a parabola-like pattern with increasing the starting maturation, and the resolute and relative laggings evolve in stage, from which the lagging depth could be predicted. The peak half-width of the hydrocarbon re-generation curve develops as the starting maturation increases, which might indicate that the hydrocarbon-derived rocks with the starting maturation lied about at oil-generated peak might be relatively high in the hydrocarbon-regenerated amount. In the meantime, the mean reactivated energy of the coal samples with starting maturation develops in four stages that are highly consistent with those of the hydrocarbon-regenerated amount and lagging, which indicated that the hydrocarbon re-generation is strictly controlled by the geochemical mechanism of the reactive kinetics.

  2. Mechanism and Kinetics Study for Photocatalytic Oxidation Degradation: A Case Study for Phenoxyacetic Acid Organic Pollutant

    Directory of Open Access Journals (Sweden)

    Kian Mun Lee

    2015-01-01

    Full Text Available Photocatalysis is a rapidly expanding technology for wastewater treatment, including a wide range of organic pollutants. Thus, understanding the kinetics and mechanism of the photocatalytic oxidation (PCO for degradation of phenoxyacetic acid (PAA is an indispensable component of risk assessment. In this study, we demonstrated that the central composite design (CCD coupled with response surface methodology (RSM was successfully employed to probe the kinetics and mechanism of PCO degradation for PAA using an efficient zinc oxide (ZnO photocatalyst. In our current case study, four independent factors such as ZnO dosage, initial concentration of PAA, solution pH, and reaction time on the PCO degradation for PAA were examined in detail. Based on our results obtained from RSM analyses, an efficient pathway leading to the high degradation rate (>90% was applying 0.4 g/L of ZnO dosage with 16 mg/L of concentration of PAA at pH 6.73 for 40 minutes. The experimental results were fitted well with the derived response model with R2 = 0.9922. This study offers a cost-effective way for probing our global environmental water pollution issue.

  3. Photo-thermo-mechanically actuated bending and snapping kinetics of liquid crystal elastomer cantilever

    International Nuclear Information System (INIS)

    A composite of liquid crystal elastomer (LCE) incorporated with carbon nanotubes (CNTs) can convert absorbed photon energy into thermal energy to trigger the phase transition of the LCE, resulting in photo-thermo-mechanically actuated devices. We model the transient temperature distribution and the bending kinetics of a straight cantilever beam actuator under the radiation of a laser diode (LD) light. Three possible bending modes of the beam for various LD light powers are identified. The temperature distribution and the bending modes are found to be in good agreement with the reported experimental observations. The underlying deformation mechanisms and bending modes are manifested by probing the stress evolution and propagation of nonzero stress regions during the bending process. For a beam that is initially slightly curved, we also predict the possibility of snap-through instability, and three typical phases of snapping are captured. This procedure paves the way for the design of LCE-based soft actuators. (paper)

  4. Kinetics and Mechanism of the Oxidation of Glycol by Dihydroxyditelluratoargentate(Ⅲ) with Spectrophotometry

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The kinetics of the oxidation of glycol by dihydroxyditelluratoargentate (Ⅲ) complex(DDA) was studied in alkaline medium with spectrophotometry(in a temperature range of 16.6-40 ℃).The first-order rates with respect to glycol and Ag(Ⅲ) were all found.The rates increased with the increase in [OH-] and decreased with the increase in [TeO2-4].No effect was found with the addition of KNO3 and no free radical was detected.In view of this,the dihydroxymonotelluratoargentate(Ⅲ) species(DMA) is assumed to be the active species.A plausible mechanism involving a two-electron transfer is proposed,and the rate equation derived from the mechanism can explain all experimental observations.Activation parameters of the rate-determining step and constants are evaluated.

  5. Kinetics and Mechanism of Oxidation of Lactic Acid by Dihydroxyditelluratoargentate(Ⅲ)in Alkaline Medium

    Institute of Scientific and Technical Information of China (English)

    SHANJin-huan; WANGLi; LIUBao-sheng; SHENShi-gang

    2003-01-01

    The kinetics of the oxidation of lactic acid(Lac) by dihydroxyditelluratoargentate(Ⅲ)[abbreviated as DDA of Ag(Ⅲ)]anions was studied in an aqueous alkaline medium by conventional spectrophotometry in a temperature range of 25-40℃.The order of the redox reaction of lactic acid and DDA was found to be first-order.The rates increased with the increase in [OH-]and decreased with the increase in [tellurate].No free radical was detected.In the view of this the dihydroxymonotelluratoargentate(Ⅲ)species(DMA) is assumed to be the active species.A plausible mechanism involving a two-electron transfer is proposed,and the rate equation derived from the mechanism can be used to explain all the experimenttal results.The activation parameters(25℃)and the rate constants of the rate-determining step along with the preequilibrium constants at different temperatures were evaluated.

  6. Kinetics and Mechanism of Oxidation of Lactic Acid by Dihydroxyditelluratoargentate(Ⅲ) in Alkaline Medium

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The kinetics of the oxidation of lactic acid(Lac) by dihydroxyditelluratoargentate(Ⅲ)[abbreviated as DDA of Ag(Ⅲ)] anions was studied in an aqueous alkaline medium by conventional spectrophotometry in a temperature range of 25—40 ℃. The order of the redox reaction of lactic acid and DDA was found to be first-order. The rates increased with the increase in [OH-] and decreased with the increase in [tellurate]. No free radical was detected. In the view of this the dihydroxymonotelluratoargentate(Ⅲ) species(DMA) is assumed to be the active species. A plausible mechanism involving a two-electron transfer is proposed, and the rate equation derived from the mechanism can be used to explain all the experimental results. The activation parameters(25 ℃) and the rate constants of the rate-determining step along with the preequilibrium constants at different temperatures were evaluated.

  7. Curing kinetics and mechanism of TDE-85/MeTHPA epoxy resin modified by polyurethane

    International Nuclear Information System (INIS)

    The TDE-85/MeTHPA epoxy resin modified by polyurethane was prepared with polyurethane prepolymer (PUP, formulated by PPG and TDI), chain-extended reagent (1,4-BDO) and crosslink agent (TMP). The curing reaction mechanism and kinetics characters of the modified resin were discussed by DSC and infrared spectrum analysis. The investigation on curing reaction mechanism indicates that polymer network I was obtained by the curing reaction between TDE-85 and MeTHPA, and polymer network II was obtained by the chain-extended and crosslinking reaction of 1,4-BDO, TMP, and PUP, meanwhile, the apparent activation energy of curing reaction decreased obviously with PU addition, and the activation energy of the resin dropped from 83.14 kJ/mol to 67.91 kJ/mol with PU modification. (authors)

  8. An equivalent finite element method to kinetics analysis of complex mechanism

    Institute of Scientific and Technical Information of China (English)

    CHE Ren-wei; LU Nian-li

    2005-01-01

    The Finite Element Method was combined with the results from considerable analysis, producing a new kinetics analysis method of EFEM for a mechanism in truss, geared system, and assembled system. The equivalent principle and the motive differential equation of the system were derived by using an equivalent element, a virtual inertia matrix, and a systematic force matrix. The element' s mass matrix expression in the two dimensional and three dimensional mechanisms of the equivalent element was determined. The equivalent mass matrixes fashion of the Jacobin matrix, generalized coordinate matrix, and equivalent forces matrix were also determined. It was validated by two examples that the new method was normal, simple and direct, and had a higher efficiency than alternative methods; this is regardless of whether traditional methods are used with differential equations and calculated by using a computer.

  9. Power optimization of chemically driven heat engine based on first and second order reaction kinetic theory and probability theory

    Science.gov (United States)

    Zhang, Lei; Chen, Lingen; Sun, Fengrui

    2016-03-01

    The finite-time thermodynamic method based on probability analysis can more accurately describe various performance parameters of thermodynamic systems. Based on the relation between optimal efficiency and power output of a generalized Carnot heat engine with a finite high-temperature heat reservoir (heat source) and an infinite low-temperature heat reservoir (heat sink) and with the only irreversibility of heat transfer, this paper studies the problem of power optimization of chemically driven heat engine based on first and second order reaction kinetic theory, puts forward a model of the coupling heat engine which can be run periodically and obtains the effects of the finite-time thermodynamic characteristics of the coupling relation between chemical reaction and heat engine on the power optimization. The results show that the first order reaction kinetics model can use fuel more effectively, and can provide heat engine with higher temperature heat source to increase the power output of the heat engine. Moreover, the power fluctuation bounds of the chemically driven heat engine are obtained by using the probability analysis method. The results may provide some guidelines for the character analysis and power optimization of the chemically driven heat engines.

  10. Kinetics and mechanism of jack bean urease inhibition by Hg2+

    Directory of Open Access Journals (Sweden)

    Du Nana

    2012-12-01

    Full Text Available Abstract Background Jack bean urease (EC 3.5.1.5 is a metalloenzyme, which catalyzes the hydrolysis of urea to produce ammonia and carbon dioxide. The heavy metal ions are common inhibitors to control the rate of the enzymatic urea hydrolysis, which take the Hg2+ as the representative. Hg2+ affects the enzyme activity causing loss of the biological function of the enzyme, which threatens the survival of many microorganism and plants. However, inhibitory kinetics of urease by the low concentration Hg2+ has not been explored fully. In this study, the inhibitory effect of the low concentration Hg2+ on jack bean urease was investigated in order to elucidate the mechanism of Hg2+ inhibition. Results According to the kinetic parameters for the enzyme obtained from Lineweaver–Burk plot, it is shown that the Km is equal to 4.6±0.3 mM and Vm is equal to 29.8±1.7 μmol NH3/min mg. The results show that the inhibition of jack bean urease by Hg2+ at low concentration is a reversible reaction. Equilibrium constants have been determined for Hg2+ binding with the enzyme or the enzyme-substrate complexes (Ki =0.012 μM. The results show that the Hg2+ is a noncompetitive inhibitor. In addition, the kinetics of enzyme inhibition by the low concentration Hg2+ has been studied using the kinetic method of the substrate reaction. The results suggest that the enzyme first reversibly and quickly binds Hg2+ and then undergoes a slow reversible course to inactivation. Furthermore, the rate constant of the forward reactions (k+0 is much larger than the rate constant of the reverse reactions (k-0. By combining with the fact that the enzyme activity is almost completely lost at high concentration, the enzyme is completely inactivated when the Hg2+ concentration is high enough. Conclusions These results suggest that Hg2+ has great impacts on the urease activity and the established inhibition kinetics model is suitable.

  11. Supporting interpretation of dynamic simulation. Application to chemical kinetic models; Aides a l`interpretation de simulations dynamiques. Application aux modeles de cinetique chimique

    Energy Technology Data Exchange (ETDEWEB)

    Braunschweig, B.

    1998-04-22

    Numerous scientific and technical domains make constant use of dynamical simulations. Such simulators are put in the hands of a growing number of users. This phenomenon is due both to the extraordinary increase in computing performance, and to better graphical user interfaces which make simulation models easy to operate. But simulators are still computer programs which produce series of numbers from other series of numbers, even if they are displayed graphically. This thesis presents new interaction paradigms between a dynamical simulator and its user. The simulator produces a self-made interpretation of its results, thanks to a dedicated representation of its domain with objects. It shows dominant cyclic mechanisms identified by their instantaneous loop gain estimates, it uses a notion of episodes for splitting the simulation into homogeneous time intervals, and completes this by animations which rely on the graphical structure of the system. These new approaches are demonstrated with examples from chemical kinetics, because of the energic and exemplary characteristics of the encountered behaviors. They are implemented in the Spike software, Software Platform for Interactive Chemical Kinetics Experiments. Similar concepts are also shown in two other domains: interpretation of seismic wave propagation, and simulation of large projects. (author) 95 refs.

  12. Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks

    Energy Technology Data Exchange (ETDEWEB)

    Ziaul Huque

    2007-08-31

    This is the final technical report for the project titled 'Mathematically Reduced Chemical Reaction Mechanism Using Neural Networks'. The aim of the project was to develop an efficient chemistry model for combustion simulations. The reduced chemistry model was developed mathematically without the need of having extensive knowledge of the chemistry involved. To aid in the development of the model, Neural Networks (NN) was used via a new network topology known as Non-linear Principal Components Analysis (NPCA). A commonly used Multilayer Perceptron Neural Network (MLP-NN) was modified to implement NPCA-NN. The training rate of NPCA-NN was improved with the GEneralized Regression Neural Network (GRNN) based on kernel smoothing techniques. Kernel smoothing provides a simple way of finding structure in data set without the imposition of a parametric model. The trajectory data of the reaction mechanism was generated based on the optimization techniques of genetic algorithm (GA). The NPCA-NN algorithm was then used for the reduction of Dimethyl Ether (DME) mechanism. DME is a recently discovered fuel made from natural gas, (and other feedstock such as coal, biomass, and urban wastes) which can be used in compression ignition engines as a substitute for diesel. An in-house two-dimensional Computational Fluid Dynamics (CFD) code was developed based on Meshfree technique and time marching solution algorithm. The project also provided valuable research experience to two graduate students.

  13. Mechanism of plasma ignition in electrothermal-chemical launcher

    Institute of Scientific and Technical Information of China (English)

    Yong JIN; Yan-jie NI; Hai-yuan LI; Bao-ming LI

    2016-01-01

    Plasma generator is a core component in an electrothermal-chemical (ETC) launcher. Its work state directly influences the launch efficiency of a system. The interaction between plasma and propellants is a very important mechanism in ETC technology. Based on the transient radiation model and open air plasma jet experiment, the mechanism of plasma ignition process is analyzed. Results show that the surface temperature of local solid propellant grain can quickly achieve the ignition temperature under the action of early transient plasma radiation. But it needs enough time to maintain the high energy flow to make self-sustained combustion of solid propellant grains. Because of the limited space characteristics of transient radiation, the near-field propellant grains can gain enough energy by the strong transient radiation to be ignited and achieve self-sustained combustion. The far-field propellant grains mainly gain the energy by the activated particles in plasma jet to be ignited and self-sustained combustion. Experiments show that plasma jet always has a high flow velocity in the area of the cartridge. Compared with conventional ignition, the solid propellant grains can obtain more quick and uniform ignition and self-sustained combustion by this kind of ablation controlled arc (ACA) plasma via energy skin effect of propellant grains, pre-heat temperature mechanism and high efficient jet diffusion.

  14. Mechanism of plasma ignition in electrothermal-chemical launcher

    Directory of Open Access Journals (Sweden)

    Yong Jin

    2016-04-01

    Full Text Available Plasma generator is a core component in an electrothermal-chemical (ETC launcher. Its work state directly influences the launch efficiency of a system. The interaction between plasma and propellants is a very important mechanism in ETC technology. Based on the transient radiation model and open air plasma jet experiment, the mechanism of plasma ignition process is analyzed. Results show that the surface temperature of local solid propellant grain can quickly achieve the ignition temperature under the action of early transient plasma radiation. But it needs enough time to maintain the high energy flow to make self-sustained combustion of solid propellant grains. Because of the limited space characteristics of transient radiation, the near-field propellant grains can gain enough energy by the strong transient radiation to be ignited and achieve self-sustained combustion. The far-field propellant grains mainly gain the energy by the activated particles in plasma jet to be ignited and self-sustained combustion. Experiments show that plasma jet always has a high flow velocity in the area of the cartridge. Compared with conventional ignition, the solid propellant grains can obtain more quick and uniform ignition and self-sustained combustion by this kind of ablation controlled arc (ACA plasma via energy skin effect of propellant grains, pre-heat temperature mechanism and high efficient jet diffusion.

  15. Correlation of Impact Conditions, Interface Reactions, Microstructural Evolution, and Mechanical Properties in Kinetic Spraying of Metals: A Review

    Science.gov (United States)

    Kim, Jaeick; Lee, Changhee

    2016-09-01

    In the past, most studies into kinetic spraying technology focused on basic research, but a large portion of current research is devoted to industrial applications of the technology. To advance, however, studies about industrial applications of kinetic spraying require profound understanding of the scientific foundations of the kinetic spray process. Nevertheless, no one has yet provided a well-organized summary of the correlations among impact conditions, interface reactions, microstructural evolution, and mechanical properties across the whole field of kinetic spraying technology. This paper provides such an overview of these correlations for kinetic spraying of metals. For each correlation, the interactions between the given conditions and the material properties of the metal feedstock powder are the most influential. These interactions are so complicated that it is difficult to systematically classify all cases into certain types. Nonetheless, we try to explain and summarize the critical factors and their roles in each relationship.

  16. 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.

  17. Kinetic studies of chemical shrinkage and residual stress formation in thermoset epoxy adhesives under confined curing conditions

    Science.gov (United States)

    Schumann, M.; Geiß, P. L.

    2015-05-01

    Faultless processing of thermoset polymers in demanding applications requires a profound mastering of the curing kinetics considering both the physico-chemical changes in the transition from the liquid to the solid state and the consolidation of the polymers network in the diffusion controlled curing regime past the gel point. Especially in adhesive joints shrinkage stress occurring at an early state of the curing process under confined conditions is likely to cause defects due to local debonding and thus reduce their strength and durability1. Rheometry is considered the method of choice to investigate the change of elastic and viscous properties in the progress of curing. Drawbacks however relate to experimental challenges in accessing the full range of kinetic parameters of thermoset resins with low initial viscosity from the very beginning of the curing reaction to the post-cure consolidation of the polymer due to the formation of secondary chemical bonds. Therefore the scope of this study was to interrelate rheological data with results from in-situ measurements of the shrinkage stress formation in adhesive joints and with the change of refractive index in the progress of curing. This combination of different methods has shown to be valuable in gaining advanced insight into the kinetics of the curing reaction. The experimental results are based on a multi component thermoset epoxy-amine adhesive.

  18. In vitro kinetic studies on the mechanism of oxygen-dependent cellular uptake of copper radiopharmaceuticals

    International Nuclear Information System (INIS)

    The development of hypoxia-selective radiopharmaceuticals for use as therapeutic and/or imaging agents is of vital importance for both early identification and treatment of cancer and in the design of new drugs. Radiotracers based on copper for use in positron emission tomography have received great attention due to the successful application of copper(II) bis(thiosemicarbazonato) complexes, such as [60/62/64Cu(II)ATSM] and [60/62/64Cu(II)PTSM], as markers for tumour hypoxia and blood perfusion, respectively. Recent work has led to the proposal of a revised mechanism of hypoxia-selective cellular uptake and retention of [Cu(II)ATSM]. The work presented here describes non-steady-state kinetic simulations in which the reported pO2-dependent in vitro cellular uptake and retention of [64Cu(II)ATSM] in EMT6 murine carcinoma cells has been modelled by using the revised mechanistic scheme. Non-steady-state (NSS) kinetic analysis reveals that the model is in very good agreement with the reported experimental data with a root-mean-squared error of less than 6% between the simulated and experimental cellular uptake profiles. Estimated rate constants are derived for the cellular uptake and washout (k1 = 9.8 ± 0.59 x 10-4 s-1 and k2 = 2.9 ± 0.17 x 10-3 s-1), intracellular reduction (k3 = 5.2 ± 0.31 x 10-2 s-1), reoxidation (k4 = 2.2 ± 0.13 mol-1 dm3 s-1) and proton-mediated ligand dissociation (k5 = 9.0 ± 0.54 x 10-5 s-1). Previous mechanisms focused on the reduction and reoxidation steps. However, the data suggest that the origins of hypoxia-selective retention may reside with the stability of the copper(I) anion with respect to protonation and ligand dissociation. In vitro kinetic studies using the nicotimamide adenine dinucleotide (NADH)-dependent ferredoxin reductase enzyme PuR isolated from the bacterium Rhodopseudomonas palustris have also been conducted. NADH turnover frequencies are found to be dependent on the structure of the ligand and the results confirm that

  19. Chemical degradation mechanisms of membranes for alkaline membrane fuel cells

    International Nuclear Information System (INIS)

    Chemical degradation mechanisms of membranes for alkaline membrane fuel cells have been investigated using density functional theory (DFT). We have elucidated that the aryl-ether moiety of membranes is one of the weakest site against attack of hydroxide ions. The results of DFT calculations for hydroxide initiated aryl-ether cleavage indicated that the aryl-ether cleavage occurred prior to degradation of cationic functional group. Such a weak nature of the aryl-ether group arises from the electron deficiency of the aryl group as well as the low bond dissociation energy. The DFT results suggests that removal of the aryl-ether group in the membrane should enhance the stability of membranes under alkaline conditions. In fact, an ether fee poly(phenylene) membrane exhibits excellent stability against the attack from hydroxide ions

  20. Chemical degradation mechanisms of membranes for alkaline membrane fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Choe, Yoong-Kee [National Institute of Advanced Industrial Science and Technology, Umezono 1-1-1, Tsukuba (Japan); Henson, Neil J.; Kim, Yu Seung [Los Alamos National Laboratory, Los Alamos, NM (United States)

    2015-12-31

    Chemical degradation mechanisms of membranes for alkaline membrane fuel cells have been investigated using density functional theory (DFT). We have elucidated that the aryl-ether moiety of membranes is one of the weakest site against attack of hydroxide ions. The results of DFT calculations for hydroxide initiated aryl-ether cleavage indicated that the aryl-ether cleavage occurred prior to degradation of cationic functional group. Such a weak nature of the aryl-ether group arises from the electron deficiency of the aryl group as well as the low bond dissociation energy. The DFT results suggests that removal of the aryl-ether group in the membrane should enhance the stability of membranes under alkaline conditions. In fact, an ether fee poly(phenylene) membrane exhibits excellent stability against the attack from hydroxide ions.

  1. Chemical and Mechanical processes during burial diagenesis of chalk

    DEFF Research Database (Denmark)

    Borre, Mai Kirstine; Lind, Ida

    1998-01-01

    or larger influence on the textural development. In the chalk interval below, compaction is not the only porosity reducing agent but it has a larger influence on texture than concurrent recrystallization. Below 850 m grain-bridging cementation becomes important resulting in a lithified limestone below 1100......Burial diagenesis of chalk is a combination of mechanical compaction and chemical recrystallization as well as cementation. We have predicted the characteristic trends in specific surface resulting from these processes. The specific surface is normally measured by nitrogen adsorption but is here...... in the Pacific, where a > 1 km thick package of chalk facies sediments accumulated from the Cretaceous to the present. In the upper 200-300 m the sediment is unconsolidated carbonate ooze, throughout this depth interval compaction is the principal porosity reducing agent, but recrystallization has an equal...

  2. SURFACE CHEMKIN-III: A Fortran package for analyzing heterogeneous chemical kinetics at a solid-surface - gas-phase interface

    Energy Technology Data Exchange (ETDEWEB)

    Coltrin, M.E.; Kee, R.J.; Rupley, F.M.; Meeks, E.

    1996-05-01

    This document is the user`s manual for the SURFACE CHEMKIN-III package. Together with CHEMKIN-III, this software facilitates the formation, solution, and interpretation of problems involving elementary heterogeneous and gas-phase chemical kinetics in the presence of a solid surface. The package consists of two major software components: an Interpreter and a Surface Subroutine Library. The Interpreter is a program that reads a symbolic description of a user-specified chemical reaction mechanism. One output from the Interpreter is a data file that forms a link to the Surface Subroutine Library, which is a collection of about seventy modular Fortran subroutines that may be called from a user`s application code to return information on chemical production rates and thermodynamic properties. This version of SURFACE CHEMKIN-III includes many modifications to allow treatment of multi-fluid plasma systems, for example modeling the reactions of highly energetic ionic species with a surface. Optional rate expressions allow reaction rates to depend upon ion energy rather than a single thermodynamic temperature. In addition, subroutines treat temperature as an array, allowing an application code to define a different temperature for each species. This version of SURFACE CHEMKIN-III allows use of real (non-integer) stoichiometric coefficients; the reaction order with respect to species concentrations can also be specified independent of the reaction`s stoichiometric coefficients. Several different reaction mechanisms can be specified in the Interpreter input file through the new construct of multiple materials.

  3. Mechanism of Interaction between Ionizing Radiation and Chemicals

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jin Kyu; Lee, B. H.; Shin, H. S. (and others)

    2008-03-15

    This research project has been carried out jointly with INP (Poland) to develop technologies for 'Mechanism of Interaction between ionizing radiation and chemicals{sup .} Several biological end-points were assessed in experimental organisms such as higher plants, rats, cell lines and yeast cells to establish proper bioassay techniques. The Tradescantia somatic cell mutation assay was carried out, and immunohistochemistry and hormone assays were done in Fisher 344 rats and cell lines to analyse the combined effect of ionizing radiation with mercury chloride. Using the common regularities of combined actions of two factors, a theoretical model was established, and applied to the thermo radiation action and synergism between two chemicals, as well. The model approach made it possible to predict the condition under which the maximum synergism could be attained. The research results were published in high standard journals and presented in the scientific conferences to verify KAERI's current technology level. The experience of collaboration can be used as a fundamental tool for multinational collaboration, and make the role of improving relationship between Korea and Poland.

  4. Mechanism of Interaction between Ionizing Radiation and Chemicals

    International Nuclear Information System (INIS)

    This research project has been carried out jointly with INP (Poland) to develop technologies for 'Mechanism of Interaction between ionizing radiation and chemicals. Several biological end-points were assessed in experimental organisms such as higher plants, rats, cell lines and yeast cells to establish proper bioassay techniques. The Tradescantia somatic cell mutation assay was carried out, and immunohistochemistry and hormone assays were done in Fisher 344 rats and cell lines to analyse the combined effect of ionizing radiation with mercury chloride. Using the common regularities of combined actions of two factors, a theoretical model was established, and applied to the thermo radiation action and synergism between two chemicals, as well. The model approach made it possible to predict the condition under which the maximum synergism could be attained. The research results were published in high standard journals and presented in the scientific conferences to verify KAERI's current technology level. The experience of collaboration can be used as a fundamental tool for multinational collaboration, and make the role of improving relationship between Korea and Poland

  5. The effect of local thermal fluctuations on the folding kinetics: a study from the perspective of the nonextensive statistical mechanics

    CERN Document Server

    Molin, J P Dal; Caliri, A

    2010-01-01

    Protein folding is a universal process, very fast and accurate, which works consistently (as it should be) in a wide range of physiological conditions. The present work is based on three premises, namely: ($i$) folding reaction is a process with two consecutive and independent stages, namely the search mechanism and the overall productive stabilization; ($ii$) the folding kinetics results from a mechanism as fast as can be; and ($iii$) at nanoscale dimensions, local thermal fluctuations may have important role on the folding kinetics. Here the first stage of folding process (search mechanism) is focused exclusively. The effects and consequences of local thermal fluctuations on the configurational kinetics, treated here in the context of non extensive statistical mechanics, is analyzed in detail through the dependence of the characteristic time of folding ($\\tau$) on the temperature $T$ and on the nonextensive parameter $q$.The model used consists of effective residues forming a chain of 27 beads, which occupy...

  6. Kinetics and Mechanism of Oxidation of Phenyl Acetic Acid and Dl-Mandelic Acid by Permanganate in Acid Medium

    OpenAIRE

    B. Syama Sundar; P.S.Radhakrishna murti

    2014-01-01

    Kinetics of oxidation of phenyl acetic acid and DL- Mandelic acid by potassium permanganate in aqueous acetic acid and perchloric acid mixture reveals that the kinetic orders are first order in oxidant, first order in H+ and zero order in substrate for phenyl acetic acid. DL-Mandelic acid exhibits first order in oxidant and zero order in substrate. The results are rationalised by a mechanism involving intermediate formation of mandelic acid in case of Phenyl acetic acid and ester formation wi...

  7. [Mechanism and kinetics of phenol degradation by TiO2 photocatalytic combined technologies].

    Science.gov (United States)

    Zhang, Yi; Huang, Ruo-Nan; Wang, Xiao-Min; Wang, Qi; Cong, Yan-Qing

    2013-02-01

    The combination H2O2, or electrical catalytic (EC) system with TiO2 photbcatalytic system for phenol degradation was investigated. The catalytic systems of TiO2/UV, H2O2/UV, TiO2/UV/H2O2 and TiO2/UV/EC were compared to investigate the phenol degradation mechanism and kinetic model. The degradation of phenol in TiO2/UV/H2O2 and TiO2/UV/EC system is more effective than that in TiO2/UV system. With the solution pH of 6, TiO, concentration of 0.2 g.L-1, UV illumination of 2 h, the photocatalysis removal efficiency of phenol reaches to 86%, if the current density of 12 mA.cm-2 is added, the removal efficiency of phenol could reach to 100%. The energy utilization in different catalytic systems was also compared. When phenol is degraded in 15 min, in TiO2/UV/EC system the energy utilization is the highest of 0.0306 g.(kW. h)-1 with the energy consumption of 0.0640 kW.h-1. It indicates that much more energy is used in TiO2/UV/EC system for phenol degradation. During the analysis of intermediate products in different catalysis systems, the first-order kinetic model of phenol degradation and intermediate products such as hydroquinone, catechol and benzoquinone formation were established. The kinetic model is validated the phenol degradation pathway in different catalysis systems, and also indicates the TiO2/UV/EC system could enhance phenol and intermediate products degradation.

  8. DNA unwinding step-size of E. coli RecBCD helicase determined from single turnover chemical quenched-flow kinetic studies.

    Science.gov (United States)

    Lucius, Aaron L; Vindigni, Alessandro; Gregorian, Razmic; Ali, Janid A; Taylor, Andrew F; Smith, Gerald R; Lohman, Timothy M

    2002-11-29

    The mechanism by which Escherichia coli RecBCD DNA helicase unwinds duplex DNA was examined in vitro using pre-steady-state chemical quenched-flow kinetic methods. Single turnover DNA unwinding experiments were performed by addition of ATP to RecBCD that was pre-bound to a series of DNA substrates containing duplex DNA regions ranging from 24 bp to 60 bp. In each case, the time-course for formation of completely unwound DNA displayed a distinct lag phase that increased with duplex length, reflecting the transient formation of partially unwound DNA intermediates during unwinding catalyzed by RecBCD. Quantitative analysis of five independent sets of DNA unwinding time courses indicates that RecBCD unwinds duplex DNA in discrete steps, with an average unwinding "step-size", m=3.9(+/-1.3)bp step(-1), with an average unwinding rate of k(U)=196(+/-77)steps s(-1) (mk(U)=790(+/-23)bps(-1)) at 25.0 degrees C (10mM MgCl(2), 30 mM NaCl (pH 7.0), 5% (v/v) glycerol). However, additional steps, not linked directly to DNA unwinding are also detected. This kinetic DNA unwinding step-size is similar to that determined for the E.coli UvrD helicase, suggesting that these two SF1 superfamily helicases may share similar mechanisms of DNA unwinding. PMID:12445778

  9. The science conceptions of chemical textbooks addressed to the high school, in treatment of chemical kinetics during the period from 1929 to 2004

    Directory of Open Access Journals (Sweden)

    Maria Eunice Ribeiro Marcondes

    2009-12-01

    Full Text Available This text is a part of the work that was developed based on the chemical kinetic theme and the target was how the scientific knowledge in this subject was used for high school textbooks, identifying the possible ideas about science related to these books. For that, based on the research developed by Níaz (1994 that used categories to represent the philosophical perspectives: the empirical/inductive and the rationalist, verifying which and how the concepts of science was inserted in the 20 Brazilians textbooks, edited in the period from 1929 to 2004.

  10. The science conceptions of chemical textbooks addressed to the high school, in treatment of chemical kinetics during the period from 1929 to 2004

    OpenAIRE

    Maria Eunice Ribeiro Marcondes; Simone Alves de Assis Martorano

    2009-01-01

    This text is a part of the work that was developed based on the chemical kinetic theme and the target was how the scientific knowledge in this subject was used for high school textbooks, identifying the possible ideas about science related to these books. For that, based on the research developed by Níaz (1994) that used categories to represent the philosophical perspectives: the empirical/inductive and the rationalist, verifying which and how the concepts of science was inserted in the 20 Br...

  11. Temperature buffer test. Hydro-mechanical and chemical/ mineralogical characterizations

    Energy Technology Data Exchange (ETDEWEB)

    Aakesson, Mattias; Olsson, Siv; Dueck, Ann; Nilsson, Ulf; Karnland, Ola [Clay Technology AB, Lund (Sweden); Kiviranta, Leena; Kumpulainen, Sirpa [BandTech Oy, Helsinki (Finland); Linden, Johan [Aabo Akademi, Aabo (Finland)

    2012-01-15

    The Temperature Buffer Test (TBT) is a joint project between SKB/ANDRA and supported by ENRESA (modeling) and DBE (instrumentation), which aims at improving the understanding and to model the thermo-hydro-mechanical behavior of buffers made of swelling clay submitted to high temperatures (over 100 deg C) during the water saturation process. The test has been carried out in a KBS-3 deposition hole at Aspo HRL. It was installed during the spring of 2003. Two steel heaters (3 m long, 0.6 m diameter) and two buffer arrangements have been investigated: the lower heater was surrounded by rings of compacted Wyoming bentonite only, whereas the upper heater was surrounded by a composite barrier, with a sand shield between the heater and the bentonite. The test was dismantled and sampled during the winter of 2009/2010. This report presents the hydro-mechanical and chemical/mineralogical characterization program which was launched subsequent to the dismantling operation. The main goal has been to investigate if any significant differences could be observed between material from the field experiment and the reference material. The field samples were mainly taken from Ring 4 (located at the mid-section around the lower heater), in which the temperature in the innermost part reached 155 deg C. The following hydro-mechanical properties have been determined for the material (test technique within brackets): hydraulic conductivity (swelling pressure device), swelling pressure (swelling pressure device), unconfined compression strength (mechanical press), shear strength (triaxial cell) and retention properties (jar method). The following chemical/mineralogical properties (methods within brackets) were determined: anion analysis of water leachates (IC), chemical composition (ICP/AES+MS, EGA), cation exchange capacity (CEC, Cu-trien method) and exchangeable cations (exchange with NH4, ICPAES), mineralogical composition (XRD and FTIR), element distribution and microstructure (SEM and

  12. Modelling cycle to cycle variations in an SI engine with detailed chemical kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Etheridge, Jonathan; Mosbach, Sebastian; Kraft, Markus [Department of Chemical Engineering and Biotechnology, University of Cambridge (United Kingdom); Wu, Hao; Collings, Nick [Department of Engineering, University of Cambridge (United Kingdom)

    2011-01-15

    This paper presents experimental results and a new computational model that investigate cycle to cycle variations (CCV) in a spark ignition (SI) engine. An established stochastic reactor model (SRM) previously used to examine homogeneous charge compression ignition (HCCI) combustion has been extended by spark initiation, flame propagation and flame termination sub-models in order to simulate combustion in SI engines. The model contains a detailed chemical mechanism but relatively short computation times are achieved. The flame front is assumed to be spherical and centred at the spark location, and a pent roof and piston bowl geometry are accounted for. The model is validated by simulating the pressure profile and emissions from an iso-octane fuelled single cylinder research engine that showed low CCV. The effects of key parameters are investigated. Experimental results that show cycle to cycle fluctuations in a four-cylinder naturally aspirated gasoline fuelled SI engine are presented. The model is then coupled with GT-Power, a one-dimensional engine simulation tool, which is used to simulate the breathing events during a multi-cycle simulation. This allows an investigation of the cyclic fluctuations in peak pressure. The source and magnitude of nitric oxide (NO) emissions produced by different cycles are then investigated. It was found that faster burning cycles result in increased NO emissions compared with cycles that have a slower rate of combustion and that more is produced in the early stages of combustion compared with later in the cycle. The majority of NO was produced via the thermal mechanism just after combustion begins. (author)

  13. Stochastic mechano-chemical kinetics of molecular motors: A multidisciplinary enterprise from a physicist’s perspective

    International Nuclear Information System (INIS)

    A molecular motor is made of either a single macromolecule or a macromolecular complex. Just like their macroscopic counterparts, molecular motors “transduce” input energy into mechanical work. All the nano-motors considered here operate under isothermal conditions far from equilibrium. Moreover, one of the possible mechanisms of energy transduction, called Brownian ratchet, does not even have any macroscopic counterpart. But, molecular motor is not synonymous with Brownian ratchet; a large number of molecular motors execute a noisy power stroke, rather than operating as Brownian ratchet. We review not only the structural design and stochastic kinetics of individual single motors, but also their coordination, cooperation and competition as well as the assembly of multi-module motors in various intracellular kinetic processes. Although all the motors considered here execute mechanical movements, efficiency and power output are not necessarily good measures of performance of some motors. Among the intracellular nano-motors, we consider the porters, sliders and rowers, pistons and hooks, exporters, importers, packers and movers as well as those that also synthesize, manipulate and degrade “macromolecules of life”. We review mostly the quantitative models for the kinetics of these motors. We also describe several of those motor-driven intracellular stochastic processes for which quantitative models are yet to be developed. In part I, we discuss mainly the methodology and the generic models of various important classes of molecular motors. In part II, we review many specific examples emphasizing the unity of the basic mechanisms as well as diversity of operations arising from the differences in their detailed structure and kinetics. Multi-disciplinary research is presented here from the perspective of physicists

  14. Molecular mechanisms of Tetranychus urticae chemical adaptation in hop fields.

    Science.gov (United States)

    Piraneo, Tara G; Bull, Jon; Morales, Mariany A; Lavine, Laura C; Walsh, Douglas B; Zhu, Fang

    2015-01-01

    The two-spotted spider mite, Tetranychus urticae Koch is a major pest that feeds on >1,100 plant species. Many perennial crops including hop (Humulus lupulus) are routinely plagued by T. urticae infestations. Hop is a specialty crop in Pacific Northwest states, where 99% of all U.S. hops are produced. To suppress T. urticae, growers often apply various acaricides. Unfortunately T. urticae has been documented to quickly develop resistance to these acaricides which directly cause control failures. Here, we investigated resistance ratios and distribution of multiple resistance-associated mutations in field collected T. urticae samples compared with a susceptible population. Our research revealed that a mutation in the cytochrome b gene (G126S) in 35% tested T. urticae populations and a mutation in the voltage-gated sodium channel gene (F1538I) in 66.7% populations may contribute resistance to bifenazate and bifenthrin, respectively. No mutations were detected in Glutamate-gated chloride channel subunits tested, suggesting target site insensitivity may not be important in our hop T. urticae resistance to abamectin. However, P450-mediated detoxification was observed and is a putative mechanism for abamectin resistance. Molecular mechanisms of T. urticae chemical adaptation in hopyards is imperative new information that will help growers develop effective and sustainable management strategies. PMID:26621458

  15. Kinetics and fracture resistance of lithiated silicon nanostructure pairs controlled by their mechanical interaction

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Seok Woo; /Stanford U., Geballe Lab.; Lee, Hyun-Wook; /Stanford U., Materials Sci. Dept.; Ryu, Ill; /Brown U.; Nix, William D.; /Stanford U., Materials Sci. Dept.; Gao, Huajian; /Brown U.; Cui, Yi; /Stanford U., Materials Sci. Dept. /SLAC

    2015-06-01

    Following an explosion of studies of silicon as a negative electrode for Li-ion batteries, the anomalous volumetric changes and fracture of lithiated single Si particles have attracted significant attention in various fields, including mechanics. However, in real batteries, lithiation occurs simultaneously in clusters of Si in a confined medium. Hence, understanding how the individual Si structures interact during lithiation in a closed space is necessary. Herein, we demonstrate physical/mechanical interactions of swelling Si structures during lithiation using well-defined Si nanopillar pairs. Ex situ SEM and in situ TEM studies reveal that compressive stresses change the reaction kinetics so that preferential lithiation occurs at free surfaces when the pillars are mechanically clamped. Such mechanical interactions enhance the fracture resistance of This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, under Contract No. DE-AC02-76SF00515. SLAC-PUB-16300 2 lithiated Si by lessening the tensile stress concentrations in Si structures. This study will contribute to improved design of Si structures at the electrode level for high performance Li-ion batteries.

  16. Mechanism and kinetics of 2-chlorophenol decomposition using coupled ultrasound and electrocatalysis

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A coupled ultrasound/electrocatalysis(US/EC) process was used to enhance the decomposition effi-ciency of organics.The synergetic kinetics and the mechanism of 2-chlorophenol(2-CP) decomposi-tion with coupled US/EC were studied.It was found that in a US/EC process 2-CP is attacked by active radicals(such as hydroxyl radicals) to form 2-chloro-p-benzoquinone,and the latter is oxidized to simple organic acids when the ring is opened.The enhancement factor expressed by the apparent rate constant of 2-CP decomposition with coupled US/EC is 1.324 at a current density of 20 mA·cm-2,an ultrasonic frequency of 20 kHz,an ultrasonic intensity of 0.27 W·cm-2,and a 2-CP initial concentration of 200 mg·L-1,which means that a synergetic effect exists.A model derived from Langmuir adsorption theory of solid surface and reaction kinetics equations can describe exactly the decomposition of 2-CP with coupled US/EC.The numerical values are in good agreement with the experimental data.The model parameters are associated with reaction conditions.

  17. Degradation of oxcarbazepine by UV-activated persulfate oxidation: kinetics, mechanisms, and pathways.

    Science.gov (United States)

    Bu, Lingjun; Zhou, Shiqing; Shi, Zhou; Deng, Lin; Li, Guangchao; Yi, Qihang; Gao, Naiyun

    2016-02-01

    The degradation kinetics and mechanism of the antiepileptic drug oxcarbazepine (OXC) by UV-activated persulfate oxidation were investigated in this study. Results showed that UV/persulfate (UV/PS) process appeared to be more effective in degrading OXC than UV or PS alone. The OXC degradation exhibited a pseudo-first order kinetics pattern and the degradation rate constants (k obs) were affected by initial OXC concentration, PS dosage, initial pH, and humic acid concentration to different degrees. It was found that low initial OXC concentration, high persulfate dosage, and initial pH enhanced the OXC degradation. Additionally, the presence of humic acid in the solution could greatly inhibit the degradation of OXC. Moreover, hydroxyl radical (OH•) and sulfate radical (SO4 (-)••) were identified to be responsible for OXC degradation and SO4 (-)• made the predominant contribution in this study. Finally, major intermediate products were identified and a preliminary degradation pathway was proposed. Results demonstrated that UV/PS system is a potential technology to control the water pollution caused by emerging contaminants such as OXC.

  18. Cr(VI) Adsorption on Red Mud Modified by Lanthanum: Performance, Kinetics and Mechanisms

    Science.gov (United States)

    Cui, You-Wei; Li, Jie; Du, Zhao-Fu; Peng, Yong-Zhen

    2016-01-01

    Water pollution caused by the highly toxic metal hexavalent chromium (Cr(VI)) creates significant human health and ecological risks. In this study, a novel adsorbent was used to treat Cr(VI)-containing wastewater; the adsorbent was prepared using red mud (RM) generated from the alumina production industry and the rare earth element lanthanum. This study explored adsorption performance, kinetics, and mechanisms. Results showed that the adsorption kinetics of the RM modified by lanthanum (La-RM), followed the pseudo-second-order model, with a rapid adsorption rate. Cr(VI) adsorption was positively associated with the absorbent dose, pH, temperature, and initial Cr(VI) concentration; coexisting anions had little impact. The maximum Cr(VI) adsorption capacity was 17.35 mg/g. Cr(VI) adsorption on La-RM was a mono-layer adsorption pattern, following the Langmuir isotherm model. Thermodynamic parameters showed the adsorption was spontaneous and endothermic. The adsorption of Cr(VI) on La-RM occurred as a result of LaOCl formation on the RM surface, which in turn further reacted with Cr(VI) in the wastewater. This study highlighted a method for converting industrial waste into a valuable material for wastewater treatment. The novel absorbent could be used as a potential adsorbent for treating Cr(VI)-contaminating wastewater, due to its cost-effectiveness and high adsorption capability. PMID:27658113

  19. Application potential of grapefruit peel as dye sorbent: Kinetics, equilibrium and mechanism of crystal violet adsorption

    Energy Technology Data Exchange (ETDEWEB)

    Saeed, Asma, E-mail: asmadr@wol.net.pk [Environmental Biotechnology Group, Biotechnology and Food Research Centre, PCSIR Laboratories Complex, Ferozepur Road, Lahore 54600 (Pakistan); Sharif, Mehwish [School of Biological Sciences, University of the Punjab, Lahore 54590 (Pakistan); Iqbal, Muhammad [Environmental Biotechnology Group, Biotechnology and Food Research Centre, PCSIR Laboratories Complex, Ferozepur Road, Lahore 54600 (Pakistan)

    2010-07-15

    This study reports the sorption of crystal violet (CV) dye by grapefruit peel (GFP), which has application potential in the remediation of dye-contaminated wastewaters using a solid waste generated by the citrus fruit juice industry. Batch adsorption of CV was conducted to evaluate the effect of initial pH, contact time, temperature, initial dye concentration, GFP adsorbent dose, and removal of the adsorbate CV dye from aqueous solution to understand the mechanism of sorption involved. Sorption equilibrium reached rapidly with 96% CV removal in 60 min. Fit of the sorption experimental data was tested on the pseudo-first and pseudo-second-order kinetics mathematical equations, which was noted to follow the pseudo-second-order kinetics better, with coefficient of correlation {>=}0.992. The equilibrium process was well described by the Langmuir isotherm model, with maximum sorption capacity of 254.16 mg g{sup -1}. The GFP was regenerated using 1 M NaOH, with up to 98.25% recovery of CV and could be reused as a dye sorbent in repeated cycles. GFP was also shown to be highly effective in removing CV from aqueous solution in continuous-flow fixed-bed column reactors. The study shows that GFP has the potential of application as an efficient sorbent for the removal of CV from aqueous solutions.

  20. Mechanism and kinetics of the NOCO reaction on Rh

    Science.gov (United States)

    Zhdanov, V. P.; Kasemo, B.

    During the past 15 years, the NOCO reaction on Rh has attracted considerable attention of the researchers working in academic and applied surface science. The practical importance of this reaction is connected with its relevance for environmental chemistry. From the point of view of academic studies, the NOCO reaction on Rh is of interest because it represents one of the simplest examples from the class of catalytic reactions occurring via decomposition of adsorbed species. At present, the detailed kinetic data for this reaction are available both for single-crystal and supported Rh, at ultrahigh vacuum (UHV) conditions and also at realistic pressures. For this reason, the NOCO reaction on Rh has become one of the major testing platforms for a microscopic, surface-science based approach to heterogeneous catalysis. The present review shows how far the progress in this field has come. In particular, the review describes in detail the evolution of the ideas for the mechanism of the reaction and also presents the data for the elementary reaction steps, obtained primarily on Rh(1 1 1) at UHV conditions. Then, the possibility of using these data for simulation of the reaction kinetics at moderate pressures, P NO ⋍ P CO ⋍ 0.01 bar, is discussed. The technological aspects of application of Rh in the automotive exhaust systems are surveyed as well, but only briefly.

  1. The mechanism and kinetic model on the OH-initiated degradation of acetofenate in the atmosphere

    Science.gov (United States)

    Kang, Lingyan; Sun, Xiaomin; Zhang, Chenxi; Zhang, Xue; Chen, Jianmin

    2015-02-01

    As an analog of DDT, acetofenate (AF), one of the organochlorine pesticides, is widely used in agricultural and mosquito sprayings. In this paper, the main reaction mechanism of AF with the OH radical and ensuing reactions are researched, including the OH-initiated reaction, oxidation reaction in the presence of O2, bimolecular reaction of AF-OH-O2 with NO/H2O, bond cleavage of aromatic ring and C7-O bond, and dehydrogenation. Among all the reaction pathways, the main products are obtained via C2-C7/C7-O bond cleavage, C3-C4/C4-C5 bond cleavage of aromatic ring, and the generation of ketene and aldehyde. The kinetic model is constructed based on the rate constants of element reactions over a temperature range of 200-600 K, which are calculated with the transition state theory method and fitted with the Arrhenius formulas. According to the kinetic model, the atmospheric lifetime of AF, is 37 days, compared to OH radical.

  2. CarD stabilizes mycobacterial open complexes via a two-tiered kinetic mechanism

    Science.gov (United States)

    Rammohan, Jayan; Ruiz Manzano, Ana; Garner, Ashley L.; Stallings, Christina L.; Galburt, Eric A.

    2015-01-01

    CarD is an essential and global transcriptional regulator in mycobacteria. While its biological role is unclear, CarD functions by interacting directly with RNA polymerase (RNAP) holoenzyme promoter complexes. Here, using a fluorescent reporter of open complex, we quantitate RPo formation in real time and show that Mycobacterium tuberculosis CarD has a dramatic effect on the energetics of RNAP bound complexes on the M. tuberculosis rrnAP3 ribosomal RNA promoter. The data reveal that Mycobacterium bovis RNAP exhibits an unstable RPo that is stabilized by CarD and suggest that CarD uses a two-tiered, concentration-dependent mechanism by associating with open and closed complexes with different affinities. Specifically, the kinetics of open-complex formation can be explained by a model where, at saturating concentrations of CarD, the rate of bubble collapse is slowed and the rate of opening is accelerated. The kinetics and open-complex stabilities of CarD mutants further clarify the roles played by the key residues W85, K90 and R25 previously shown to affect CarD-dependent gene regulation in vivo. In contrast to M. bovis RNAP, Escherichia coli RNAP efficiently forms RPo on rrnAP3, suggesting an important difference between the polymerases themselves and highlighting how transcriptional machinery can vary across bacterial genera. PMID:25697505

  3. Active mechanics reveal molecular-scale force kinetics in living oocytes

    CERN Document Server

    Ahmed, Wylie W; Almonacid, Maria; Bussonnier, Matthias; Verlhac, Marie-Helene; Gov, Nir S; Visco, Paolo; van Wijland, Frederic; Betz, Timo

    2015-01-01

    Unlike traditional materials, living cells actively generate forces at the molecular scale that change their structure and mechanical properties. This nonequilibrium activity is essential for cellular function, and drives processes such as cell division. Single molecule studies have uncovered the detailed force kinetics of isolated motor proteins in-vitro, however their behavior in-vivo has been elusive due to the complex environment inside the cell. Here, we quantify active force generation in living oocytes using in-vivo optical trapping and laser interferometry of endogenous vesicles. We integrate an experimental and theoretical framework to connect mesoscopic measurements of nonequilibrium properties to the underlying molecular-scale force kinetics. Our results show that force generation by myosin-V drives the cytoplasmic-skeleton out-of-equilibrium (at frequencies below 300 Hz) and actively softens the environment. In vivo myosin-V activity generates a force of $F \\sim 0.4$ pN, with a power-stroke of len...

  4. Degradation of oxcarbazepine by UV-activated persulfate oxidation: kinetics, mechanisms, and pathways.

    Science.gov (United States)

    Bu, Lingjun; Zhou, Shiqing; Shi, Zhou; Deng, Lin; Li, Guangchao; Yi, Qihang; Gao, Naiyun

    2016-02-01

    The degradation kinetics and mechanism of the antiepileptic drug oxcarbazepine (OXC) by UV-activated persulfate oxidation were investigated in this study. Results showed that UV/persulfate (UV/PS) process appeared to be more effective in degrading OXC than UV or PS alone. The OXC degradation exhibited a pseudo-first order kinetics pattern and the degradation rate constants (k obs) were affected by initial OXC concentration, PS dosage, initial pH, and humic acid concentration to different degrees. It was found that low initial OXC concentration, high persulfate dosage, and initial pH enhanced the OXC degradation. Additionally, the presence of humic acid in the solution could greatly inhibit the degradation of OXC. Moreover, hydroxyl radical (OH•) and sulfate radical (SO4 (-)••) were identified to be responsible for OXC degradation and SO4 (-)• made the predominant contribution in this study. Finally, major intermediate products were identified and a preliminary degradation pathway was proposed. Results demonstrated that UV/PS system is a potential technology to control the water pollution caused by emerging contaminants such as OXC. PMID:26452660

  5. Features in chemical kinetics. I. Signatures of self-emerging dimensional reduction from a general format of the evolution law

    Science.gov (United States)

    Nicolini, Paolo; Frezzato, Diego

    2013-06-01

    Simplification of chemical kinetics description through dimensional reduction is particularly important to achieve an accurate numerical treatment of complex reacting systems, especially when stiff kinetics are considered and a comprehensive picture of the evolving system is required. To this aim several tools have been proposed in the past decades, such as sensitivity analysis, lumping approaches, and exploitation of time scales separation. In addition, there are methods based on the existence of the so-called slow manifolds, which are hyper-surfaces of lower dimension than the one of the whole phase-space and in whose neighborhood the slow evolution occurs after an initial fast transient. On the other hand, all tools contain to some extent a degree of subjectivity which seems to be irremovable. With reference to macroscopic and spatially homogeneous reacting systems under isothermal conditions, in this work we shall adopt a phenomenological approach to let self-emerge the dimensional reduction from the mathematical structure of the evolution law. By transforming the original system of polynomial differential equations, which describes the chemical evolution, into a universal quadratic format, and making a direct inspection of the high-order time-derivatives of the new dynamic variables, we then formulate a conjecture which leads to the concept of an "attractiveness" region in the phase-space where a well-defined state-dependent rate function ω has the simple evolution dot{ω }= - ω ^2 along any trajectory up to the stationary state. This constitutes, by itself, a drastic dimensional reduction from a system of N-dimensional equations (being N the number of chemical species) to a one-dimensional and universal evolution law for such a characteristic rate. Step-by-step numerical inspections on model kinetic schemes are presented. In the companion paper [P. Nicolini and D. Frezzato, J. Chem. Phys. 138, 234102 (2013)], 10.1063/1.4809593 this outcome will be naturally

  6. Kinetic resolution of oxazinones: rational exploration of chemical space through the design of experiments.

    Science.gov (United States)

    Renzi, Polyssena; Kronig, Christel; Carlone, Armando; Eröksüz, Serap; Berkessel, Albrecht; Bella, Marco

    2014-09-01

    The organocatalytic kinetic resolution of 4-substituted oxazinones has been optimised (selectivity factor S up to 98, chiral oxazinone ee values up to 99.6 % (1 a-g) and product ee values up to 90 % (3 a-g)) in a rational way by applying the Design of Experiments (DoE) approach.

  7. An Analogy Using Pennies and Dimes to Explain Chemical Kinetics Concepts

    Science.gov (United States)

    Cortes-Figueroa, Jose E.; Perez, Wanda I.; Lopez, Jose R.; Moore-Russo, Deborah A.

    2011-01-01

    In this article, the authors present an analogy that uses coins and graphical analysis to teach kinetics concepts and resolve pseudo-first-order rate constants related to transition-metal complexes ligand-solvent exchange reactions. They describe an activity that is directed to upper-division undergraduate and graduate students. The activity…

  8. Kinetics and mechanism of the oxidation of substituted benzylamines by cetyltrimethylammonium permanganate

    Indian Academy of Sciences (India)

    Raghvendra Shukla; Pradeep K Sharma; László Kótai; Kalyan K Banerji

    2003-04-01

    Oxidation of meta- and para-substituted benzylamines by cetyltrimethylammonium permanganate (CTAP) to the corresponding aldimines is first order with respect to both the amine and CTAP. Oxidation of deuteriated benzylamine (PhCD2NH2) exhibited the presence of a substantial kinetic isotope effect (/ = 5.60 at 293 K). This confirmed the cleavage of an -C-H bond in the ratedetermining step. Correlation analyses of the rates of oxidation of 19 monosubstituted benzylamines were performed with various single and multiparametric equations. The rates of the oxidation showed excellent correlations in terms of Yukawa-Tsuno and Brown’s equations. The polar reaction constants are negative. The oxidation exhibited an extensive cross-conjugation, in the transition state, between the electron-donating substituents and the reaction centre. A mechanism involving a hydride-ion transfer from the amine to CTAP in the rate-determining step has been proposed.

  9. Kinetics and mechanism of the oxidation of some -hydroxy acids by hexamethylenetetramine-bromine

    Indian Academy of Sciences (India)

    Dimple Garg; Seema Kothari

    2004-11-01

    The oxidation of lactic acid, mandelic acid and ten monosubstituted mandelic acids by hexamethylenetetramine-bromine (HABR) in glacial acetic acid, leads to the formation of the corresponding oxoacid. The reaction is first order with respect to each of the hydroxy acids and HABR. It is proposed that HABR itself is the reactive oxidizing species. The oxidation of -deuteriomandelic acid exhibits the presence of a substantial kinetic isotope effect (/ = 5.91 at 298 K). The rates of oxidation of the substituted mandelic acids show excellent correlation with Brown’s + values. The reaction constants are negative. The oxidation exhibits an extensive cross conjugation between the electron-donating substituent and the reaction centre in the transition state. A mechanism involving transfer of a hydride ion from the acid to the oxidant is postulated.

  10. Evaluation of kinetic parameters and redox mechanism of quinoxaline at glassy carbon electrode

    Directory of Open Access Journals (Sweden)

    Aleksić Mara M.

    2014-01-01

    Full Text Available The electrochemical behavior of a biologically important heterocyclic compound quinoxaline (QUI was investigated by cyclic voltammetry (CV in solutions of differing pH, using a glassy carbon electrode (GCE. The reduction of QUI occurs as a quasi-reversible reaction in acid medium, reaching reversibility in alkaline solutions. The kinetic parameters of the electrode process such as αnα, diffusion coefficient (D and heterogeneous rate constant (ks, were evaluated and discussed. Redox mechanism of QUI was proposed on the basis of experimental results. Reduction process involves a transfer of two electrons and two protons at the pyrazine ring of QUI forming a dihydro-derivative. In acid solutions, the product of QUI reduction undergoes irreversible oxidation in a one-electron process. The electrode processes was found to be diffusion controlled. [Projekat Ministarstva nauke Republike Srbije, br. 172033

  11. Kinetics and mechanism of oxidation of aliphatic primary alcohols by quinolinium bromochromate

    Indian Academy of Sciences (India)

    Sonu Saraswat; Vinita Sharma; K K Banerji

    2003-02-01

    Oxidation of nine aliphatic primary alcohols by quinolinium bromochromate (QBC) in dimethylsulphoxide leads to the formation of the corresponding aldehydes. The reaction is first order with respect to both QBC and the alcohol. The reaction is catalysed by hydrogen ions. The hydrogen-ion dependence has the form: obs = + [H+]. The oxidation of [1,1-2H2]ethanol (MeCD2OH) exhibits a substantial primary kinetic isotope effect. The reaction has been studied in nineteen different organic solvents. The solvent effect was analysed using Taft’s and Swain's multiparametric equations. The rate of oxidation is susceptible to both polar and steric effects of the substituents. A suitable mechanism has been proposed.

  12. Microscopic Mechanism and Kinetics of Ice Formation at Complex Interfaces: Zooming in on Kaolinite

    Science.gov (United States)

    2016-01-01

    Most ice in nature forms because of impurities which boost the exceedingly low nucleation rate of pure supercooled water. However, the microscopic details of ice nucleation on these substances remain largely unknown. Here, we have unraveled the molecular mechanism and the kinetics of ice formation on kaolinite, a clay mineral playing a key role in climate science. We find that the formation of ice at strong supercooling in the presence of this clay is about 20 orders of magnitude faster than homogeneous freezing. The critical nucleus is substantially smaller than that found for homogeneous nucleation and, in contrast to the predictions of classical nucleation theory (CNT), it has a strong two-dimensional character. Nonetheless, we show that CNT describes correctly the formation of ice at this complex interface. Kaolinite also promotes the exclusive nucleation of hexagonal ice, as opposed to homogeneous freezing where a mixture of cubic and hexagonal polytypes is observed. PMID:27269363

  13. Spectral methods in chemistry and physics applications to kinetic theory and quantum mechanics

    CERN Document Server

    Shizgal, Bernard

    2015-01-01

    This book is a pedagogical presentation of the application of spectral and pseudospectral methods to kinetic theory and quantum mechanics. There are additional applications to astrophysics, engineering, biology and many other fields. The main objective of this book is to provide the basic concepts to enable the use of spectral and pseudospectral methods to solve problems in diverse fields of interest and to a wide audience. While spectral methods are generally based on Fourier Series or Chebychev polynomials, non-classical polynomials and associated quadratures are used for many of the applications presented in the book. Fourier series methods are summarized with a discussion of the resolution of the Gibbs phenomenon. Classical and non-classical quadratures are used for the evaluation of integrals in reaction dynamics including nuclear fusion, radial integrals in density functional theory, in elastic scattering theory and other applications. The subject matter includes the calculation of transport coefficient...

  14. Phase Transformations in CuAu: Morphologies and Kinetics from Quantum Mechanics

    Science.gov (United States)

    Elder, Ken; Chakraborty, Bulbul; Goldenfeld, Nigel

    1996-03-01

    The existence of a modulated superlattice at intermediate temperatures in CuAu gives rise to a rich and complex set of phase transformations. For example, quenches from high and low temperatures into the modulated region leads respectively to the nucleation of labyrinth and bullseye patterns. In this alloy even the formation of the ordered superlattice from a disordered phase is dramatically different than that which occurs in standard disorder/order transformations. This transformation is strongly influenced by the presence of small metastable droplets that are the size of the modulated wavelength. A theoretical description(Bulbul Chakraborty, Ken Elder and Nigel Goldenfeld, Physica A, in press (1995)) of these kinetics and morphologies will be presented and compared to experiment. This description is based on a time-dependent Ginzburg-Landau equation that was derived from a quantum mechanical Hamiltonian using the embedded atom method(Bulbul Chakraborty and Zhigang Xi, Phys. Rev. Lett 68), 2039 (1992).

  15. Mechanisms and kinetics for preparing carbohydrazide by reacting dimethyl carbonate with hydrazine: A theoretical study

    Science.gov (United States)

    Zhang, Jianguo; Feng, Lina; Zhang, Shaowen; Zheng, Hong; Zhang, Tonglai; Yang, Li; Zheng, Huihui

    The mechanism and kinetic modeling for preparing carbohydrazide from dimethyl carbonate and hydrazine has been declared. The geometries of all the stationary points (reactants, intermediates, transition states, and products) are optimized by using the B3LYP method with the cc-pVDZ basis set, and the harmonic vibrational frequencies as well as infrared intensities are predicted with the same method. The minimum-energy paths are obtained by using the intrinsic reaction coordinate (IRC) theory at the B3LYP/cc-pVDZ level of theory with the step length 0.02 (amu)1/2·bohr. The rate constants are evaluated by using the TST, TST/Eckart, and RRKM (T)/Eckart methods.

  16. Mechanism and kinetics model of hydrolysis in anaerobic digestion of kitchen wastes

    Institute of Scientific and Technical Information of China (English)

    吴云; 张代钧; 杨钢

    2009-01-01

    The profile of hydrolysates during the anaerobic digestion of kitchen wastes was investigated. The experimental results show that the hysteresis of hydrolytic rate is mainly controlled by the diffusion effect. The hydrolytic mechanism of kitchen wastes is elaborated by taking the diffusion effect into consideration. A segment model of the hydrolysis for kitchen waste is formulated including the coefficient of diffusion resistance in the model. The coefficients of diffusion resistance for different particle sizes are 1.42,2.12 and 2.78 respectively based on the experimental data,in which the coefficients of diffusion resistance conform an exponential function. So,the partitioning kinetic model could be integrated as a unified experience model. The model is verified with experimental data,which shows that the model could predict the concentration of organic substances during the anaerobic digestion of kitchen wastes.

  17. Kinetics and mechanism of the oxidation of some neutral and acidic -amino acids by tetrabutylammonium tribromide

    Indian Academy of Sciences (India)

    Raghvendra Shukla; Pradeep K Sharma; Kalyan K Banerji

    2004-03-01

    The oxidation of eleven amino acids by tetrabutylammonium tribromide (TBATB) in aqueous acetic acid results in the formation of the corresponding carbonyl compounds and ammonia. The reaction is first order with respect to TBATB. Michaelis-Menten type kinetics is observed with some of the amino acids while others exhibit second-order dependence. It failed to induce polymerization of acrylonitrile. The effect of solvent composition indicate that the rate of reaction increases with increase in the polarity of the medium. Addition of tetrabutylammonium chloride has no effect on the rate of oxidation. Addition of bromide ion causes decrease in the oxidation rate but only to a limiting value. The reaction is susceptible to both polar and steric effects of the substituents. A suitable mechanism has been proposed.

  18. Microscopic Mechanism and Kinetics of Ice Formation at Complex Interfaces: Zooming in on Kaolinite.

    Science.gov (United States)

    Sosso, Gabriele C; Li, Tianshu; Donadio, Davide; Tribello, Gareth A; Michaelides, Angelos

    2016-07-01

    Most ice in nature forms because of impurities which boost the exceedingly low nucleation rate of pure supercooled water. However, the microscopic details of ice nucleation on these substances remain largely unknown. Here, we have unraveled the molecular mechanism and the kinetics of ice formation on kaolinite, a clay mineral playing a key role in climate science. We find that the formation of ice at strong supercooling in the presence of this clay is about 20 orders of magnitude faster than homogeneous freezing. The critical nucleus is substantially smaller than that found for homogeneous nucleation and, in contrast to the predictions of classical nucleation theory (CNT), it has a strong two-dimensional character. Nonetheless, we show that CNT describes correctly the formation of ice at this complex interface. Kaolinite also promotes the exclusive nucleation of hexagonal ice, as opposed to homogeneous freezing where a mixture of cubic and hexagonal polytypes is observed. PMID:27269363

  19. Photocatalytic Degradation of Phenol Using a Nanocatalyst: The Mechanism and Kinetics

    Directory of Open Access Journals (Sweden)

    Y. Tao

    2013-01-01

    Full Text Available The study of photocatalytic degradation of phenol was exploited with nano-ZnO as immobilized photocatalysts in a laboratory scale photocatalytic reactor. The photocatalytic degradation mechanism and kinetics of phenol in water were studied using the solid-phase microextraction (SPME technique. Based on optimized headspace SPME conditions, phenol in water was first extracted by the fibre, which was subsequently inserted into an aqueous system with immobilized photocatalysts (nano-ZnO exposed to an irradiation source (i.e., ultraviolet A (UVA lamps. After different irradiation times (5–80 min, four main intermediates of photocatalytic degradation generated on the fibre were determined by GC-MS.

  20. Biosorption of Cu (II onto chemically modified waste mycelium of Aspergillus awamori: Equilibrium, kinetics and modeling studies

    Directory of Open Access Journals (Sweden)

    ZDRAVKA VELKOVA

    2012-01-01

    Full Text Available The biosorption potential of chemically modified waste mycelium of industrial xylanase-producing strain Aspergillus awamori for Cu (II removal from aqueous solutions was evaluated. The influence of pH, contact time and initial Cu (II concentration on the removal efficiency was evaluated. Maximum biosorption capacity was reached by sodium hydroxide treated waste fungal mycelium at pH 5.0. The Langmuir adsorption equation matched very well the adsorption equilibrium data in the studied conditions. The process kinetic followed the pseudo-firs order model.