WorldWideScience

Sample records for chemical kinetic simulations

  1. 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)

  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. 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)

  4. 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.

  5. Dynamic Simulation of Chemical Kinetics in Microcontroller

    Directory of Open Access Journals (Sweden)

    Renato Dutra Pereira Filho

    2014-12-01

    Full Text Available Arduino boards are interesting computational tools due to low cost and power consumption, as well as I/O ports, both analogs and digitals. Yet, small memory and clock frequency with truncation errors may disrupt numerical processing. This study aimed to design and evaluate the performance of a dynamic simulation based on ODEs in the Arduino, with three evaluated microprocessors; ATMEGA 328P and 2560, both 8 bits, and SAM3X8E Atmel ARM CORTEX – 32 bits. The study case was a batch reactor dynamic simulation. The Runge-Kutta 4th order algorithm was written in C++ and compiled for EPROM utilization. The output was a 115000bit/s serial connection. Processing time was almost identical for 8 bits architectures, while 32 bits was 25% faster. Without the serial connection the 8 bits architectures were 16 times faster and the 32 bits was 42 times faster. Error truncation was similar, since the floating points are done through software. The Arduino platform, despite its modest hardware, allows simple chemical systems simulation

  6. Chemical kinetics

    International Nuclear Information System (INIS)

    This book gives descriptions of chemical kinetics. It starts summary of chemical kinetics and reaction mechanism, and explains basic velocity law, experiment method for determination of reaction velocity, temperature dependence of reaction velocity, theory of reaction velocity, theory on reaction of unimolecular, process of atom and free radical, reaction in solution, catalysis, photochemical reaction, such as experiment and photochemical law and rapid reaction like flame, beam of molecule and shock tube.

  7. Simulation; an everyday tool for research in chemical kinetics

    International Nuclear Information System (INIS)

    In order to make apparent the facilities offered by the NEPTUNIX package in solving some complex problems in chemical kinetics, the paper deals with its application to a particular example taken from material science: assistance to the validation of mechanisms governing colloids growth in a fluorite crystal when it is irradiated by an electron beam

  8. 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

    It is desired to make detailed chemical kinetic mechanisms applicable to the complex geometries of practical combustion devices simulated with computational fluid dynamics tools. This work presents a novel general approach to combining computational fluid dynamics and a detailed chemical kinetic...... 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...

  9. 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.

  10. Large Eddy Simulation of Turbulent Combustion with Chemical Kinetics

    OpenAIRE

    Panjwani, Balram

    2011-01-01

    The present doctoral thesis studies and develops methodologies for turbulent combustion with the Large Eddy Simulation (LES). Three main objectives for present doctoral thesis were.First, development of LES methodology in curvilinear coordinates. LES formulation in curvilinear coordinates can be achieved in two ways, (1) conventional approach, where filtering is performed prior to the transformation, and (2) alternate approach, where filtering is performed after the transformation. In present...

  11. 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/. PMID:26807911

  12. Chemical Kinetic Simulation of the Combustion of Bio-based Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Ashen, Ms. Refuyat [Oak Ridge High School; Cushman, Ms. Katherine C. [Oak Ridge High School

    2007-10-01

    Due to environmental and economic issues, there has been an increased interest in the use of alternative fuels. However, before widespread use of biofuels is feasible, the compatibility of these fuels with specific engines needs to be examined. More accurate models of the chemical combustion of alternative fuels in Homogeneous Charge Compression Ignition (HCCI) engines are necessary, and this project evaluates the performance of emissions models and uses the information gathered to study the chemical kinetics involved. The computer simulations for each alternative fuel were executed using the Chemkin chemical kinetics program, and results from the runs were compared with data gathered from an actual engine that was run under similar conditions. A new heat transfer mechanism was added to the existing model's subroutine, and simulations were then conducted using the heat transfer mechanism. Results from the simulation proved to be accurate when compared with the data taken from the actual engine. The addition of heat transfer produced more realistic temperature and pressure data for biodiesel when biodiesel's combustion was simulated in an HCCI engine. The addition of the heat transfer mechanism essentially lowered the peak pressures and peak temperatures during combustion of all fuels simulated in this project.

  13. Numerical Simulation of a Reacting Vortex Ring Using Detailed Chemical Kinetics

    Science.gov (United States)

    Safta, C.; Madnia, C. K.

    1999-11-01

    A DNS study is conducted to examine the laminar flame-vortex interactions in a reacting vortex ring using `realistic' chemical kinetics. The set of equations solved is the compressible multi-species reacting flow equations comprising conservation of mass, linear momentum, energy, and species mass fractions. Transport properties for pure species were evaluated using thermo-molecular databases provided by the Chemkin library.(R.J. Kee et al.,) SANDIA Report, SAND86-8246, 1994. The mixture average formulation was used to evaluate the transport properties for the mixture. Methane combustion was simulated using GRI-Mech v1.2 kinetic model. The vortex ring was generated by a brief discharge of fuel through a round orifice which enters a quiescent ambient with the chemical composition of air. By adjusting the ratio of the ambient and fuel temperatures, the ignition delay time was controlled. The detailed kinetic mechanism will be examined to determine the ignition paths for this unsteady configuration. Time dependent correlations between fundamental parameters such as stoichiometry, heat release rate, hydrodynamic and chemical variables will be investigated to find the most appropriate flame observables for unsteady methane diffusion flames.

  14. 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...

  15. Kinetic simulation

    Institute of Scientific and Technical Information of China (English)

    C.S. Chang

    2007-01-01

    @@ The ITER relevant edge plasmas in the present day experiments are in the kinetic regime,with the pedestalions in the long-mean-free-path banans collisionality regime and the pedestal electrons in the banana-plateau regime.

  16. 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

  17. Isobutane ignition delay time measurements at high pressure and detailed chemical kinetic simulations

    Energy Technology Data Exchange (ETDEWEB)

    Healy, D.; Curran, H.J. [Combustion Chemistry Centre, School of Chemistry, NUI Galway (Ireland); Donato, N.S.; Aul, C.J.; Petersen, E.L. [Department of Mechanical Engineering, Texas A and M University, College Station, TX (United States); Zinner, C.M. [Mechanical, Materials and Aerospace Engineering, University of Central Florida, Orlando, FL (United States); Bourque, G. [Rolls-Royce Canada Limited, 9500 Cote de Liesse, Lachine, Quebec (Canada)

    2010-08-15

    Rapid compression machine and shock-tube ignition experiments were performed for real fuel/air isobutane mixtures at equivalence ratios of 0.3, 0.5, 1, and 2. The wide range of experimental conditions included temperatures from 590 to 1567 K at pressures of approximately 1, 10, 20, and 30 atm. These data represent the most comprehensive set of experiments currently available for isobutane oxidation and further accentuate the complementary attributes of the two techniques toward high-pressure oxidation experiments over a wide range of temperatures. The experimental results were used to validate a detailed chemical kinetic model composed of 1328 reactions involving 230 species. This mechanism has been successfully used to simulate previously published ignition delay times as well. A thorough sensitivity analysis was performed to gain further insight to the chemical processes occurring at various conditions. Additionally, useful ignition delay time correlations were developed for temperatures greater than 1025 K. Comparisons are also made with available isobutane data from the literature, as well as with 100% n-butane and 50-50% n-butane-isobutane mixtures in air that were presented by the authors in recent studies. In general, the kinetic model shows excellent agreement with the data over the wide range of conditions of the present study. (author)

  18. n-Butane: Ignition delay measurements at high pressure and detailed chemical kinetic simulations

    Energy Technology Data Exchange (ETDEWEB)

    Healy, D.; Curran, H.J. [Combustion Chemistry Centre, School of Chemistry, NUI Galway (Ireland); Donato, N.S.; Aul, C.J.; Petersen, E.L. [Department of Mechanical Engineering, Texas A and M University, College Station, TX (United States); Zinner, C.M. [Mechanical, Materials and Aerospace Engineering, University of Central Florida, Orlando, FL (United States); Bourque, G. [Rolls-Royce Canada Limited, 9500 Cote de Liesse, Lachine, Quebec, H8T 1A2 (Canada)

    2010-08-15

    Ignition delay time measurements were recorded at equivalence ratios of 0.3, 0.5, 1, and 2 for n-butane at pressures of approximately 1, 10, 20, 30 and 45 atm at temperatures from 690 to 1430 K in both a rapid compression machine and in a shock tube. A detailed chemical kinetic model consisting of 1328 reactions involving 230 species was constructed and used to validate the delay times. Moreover, this mechanism has been used to simulate previously published ignition delay times at atmospheric and higher pressure. Arrhenius-type ignition delay correlations were developed for temperatures greater than 1025 K which relate ignition delay time to temperature and concentration of the mixture. Furthermore, a detailed sensitivity analysis and a reaction pathway analysis were performed to give further insight to the chemistry at various conditions. When compared to existing data from the literature, the model performs quite well, and in several instances the conditions of earlier experiments were duplicated in the laboratory with overall good agreement. To the authors' knowledge, the present paper presents the most comprehensive set of ignition delay time experiments and kinetic model validation for n-butane oxidation in air. (author)

  19. 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

  20. Feasibility of Reduced Chemical Kinetic Mechanisms of Methane in Internal Combustion Engine Simulations

    Science.gov (United States)

    Ennetta, Ridha; Said, Rachid

    2008-09-01

    Three reduced chemical kinetic mechanisms of methane combustion were tested and compared with the standard detailed scheme GriMech 3.0., using the internal combustion engine (ICE) model of Chemkin 4.02 [1]. This study shows acceptable concordances in the prediction of temperature and main species profiles. But reduced schemes were incapables to predict all polluant emissions in an internal combustion engine.

  1. 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

  2. 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.

  3. 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

    Phase changes are known to cause convergence problems for integration of stiff kinetics in thermal and compositional reservoir simulations. We propose an algorithm for detection and location of phase changes based on discrete event system theory. The algorithm provides a robust way for handling the...... switching of variables and equations required when the number of phases changes. We extend the method to handle full phase equilibrium described by an equation of state. Experiments show that the new algorithm improves the robustness of the integration process near phase boundaries by lowering the number 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...

  4. 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

  5. LLNL Chemical Kinetics Modeling Group

    Energy Technology Data Exchange (ETDEWEB)

    Pitz, W J; Westbrook, C K; Mehl, M; Herbinet, O; Curran, H J; Silke, E J

    2008-09-24

    The LLNL chemical kinetics modeling group has been responsible for much progress in the development of chemical kinetic models for practical fuels. The group began its work in the early 1970s, developing chemical kinetic models for methane, ethane, ethanol and halogenated inhibitors. Most recently, it has been developing chemical kinetic models for large n-alkanes, cycloalkanes, hexenes, and large methyl esters. These component models are needed to represent gasoline, diesel, jet, and oil-sand-derived fuels.

  6. Binomial tau-leap spatial stochastic simulation algorithm for applications in chemical kinetics.

    Science.gov (United States)

    Marquez-Lago, Tatiana T; Burrage, Kevin

    2007-09-14

    In cell biology, cell signaling pathway problems are often tackled with deterministic temporal models, well mixed stochastic simulators, and/or hybrid methods. But, in fact, three dimensional stochastic spatial modeling of reactions happening inside the cell is needed in order to fully understand these cell signaling pathways. This is because noise effects, low molecular concentrations, and spatial heterogeneity can all affect the cellular dynamics. However, there are ways in which important effects can be accounted without going to the extent of using highly resolved spatial simulators (such as single-particle software), hence reducing the overall computation time significantly. We present a new coarse grained modified version of the next subvolume method that allows the user to consider both diffusion and reaction events in relatively long simulation time spans as compared with the original method and other commonly used fully stochastic computational methods. Benchmarking of the simulation algorithm was performed through comparison with the next subvolume method and well mixed models (MATLAB), as well as stochastic particle reaction and transport simulations (CHEMCELL, Sandia National Laboratories). Additionally, we construct a model based on a set of chemical reactions in the epidermal growth factor receptor pathway. For this particular application and a bistable chemical system example, we analyze and outline the advantages of our presented binomial tau-leap spatial stochastic simulation algorithm, in terms of efficiency and accuracy, in scenarios of both molecular homogeneity and heterogeneity. PMID:17867731

  7. 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.

  8. 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.

  9. 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.

  10. Analysing GCN4 translational control in yeast by stochastic chemical kinetics modelling and simulation

    Directory of Open Access Journals (Sweden)

    Romano M Carmen

    2011-08-01

    Full Text Available Abstract Background The yeast Saccharomyces cerevisiae responds to amino acid starvation by inducing the transcription factor Gcn4. This is mainly mediated via a translational control mechanism dependent upon the translation initiation eIF2·GTP·Met-tRNAiMet ternary complex, and the four short upstream open reading frames (uORFs in its 5' mRNA leader. These uORFs act to attenuate GCN4 mRNA translation under normal conditions. During amino acid starvation, levels of ternary complex are reduced. This overcomes the GCN4 translation attenuation effect via a scanning/reinitiation control mechanism dependent upon uORF spacing. Results Using published experimental data, we have developed and validated a probabilistic formulation of GCN4 translation using the Chemical Master Equation (Model 1. Model 1 explains GCN4 translation's nonlinear dependency upon uORF placements, and predicts that an as yet unidentified factor, which was proposed to regulate GCN4 translation under some conditions, only has pronounced effects upon GCN4 translation when intercistronic distances are unnaturally short. A simpler Model 2 that does not include this unidentified factor could well represent the regulation of a natural GCN4 mRNA. Using parameter values optimised for this algebraic Model 2, we performed stochastic simulations by Gillespie algorithm to investigate the distribution of ribosomes in different sections of GCN4 mRNA under distinct conditions. Our simulations demonstrated that ribosomal loading in the 5'-untranslated region is mainly determined by the ratio between the rates of 5'-initiation and ribosome scanning, but was not significantly affected by rate of ternary complex binding. Importantly, the translation rate for codons starved of cognate tRNAs is predicted to be the most significant contributor to the changes in ribosomal loading in the coding region under repressing and derepressing conditions. Conclusions Our integrated probabilistic Models 1 and 2

  11. 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.

  12. 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

  13. 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.

  14. 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

  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 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. Application of a Genetic Algorithm to the Optimization of Rate Constants in Chemical Kinetic Models for Combustion Simulation of HCCI Engines

    Science.gov (United States)

    Kim, Sang-Kyu; Ito, Kazuma; Yoshihara, Daisuke; Wakisaka, Tomoyuki

    For numerically predicting the combustion processes in homogeneous charge compression ignition (HCCI) engines, practical chemical kinetic models have been explored. A genetic algorithm (GA) has been applied to the optimization of the rate constants in detailed chemical kinetic models, and a detailed kinetic model (592 reactions) for gasoline reference fuels with arbitrary octane number between 60 and 100 has been obtained from the detailed reaction schemes for iso-octane and n-heptane proposed by Golovitchev. The ignition timing in a gasoline HCCI engine has been predicted reasonably well by zero-dimensional simulation using the CHEMKIN code with this detailed kinetic model. An original reduced reaction scheme (45 reactions) for dimethyl ether (DME) has been derived from Curran’s detailed scheme, and the combustion process in a DME HCCI engine has been predicted reasonably well in a practical computation time by three-dimensional simulation using the authors’ GTT code, which has been linked to the CHEMKIN subroutines with the proposed reaction scheme and also has adopted a modified eddy dissipation combustion model.

  18. Study of ignition in a high compression ratio SI (spark ignition) methanol engine using LES (large eddy simulation) with detailed chemical kinetics

    International Nuclear Information System (INIS)

    Methanol has been recently used as an alternative to conventional fuels for internal combustion engines in order to satisfy some environmental and economical concerns. In this paper, the ignition in a high compression ratio SI (spark ignition) methanol engine was studied by using LES (large eddy simulation) with detailed chemical kinetics. A 21-species, 84-reaction methanol mechanism was adopted to simulate the auto-ignition process of the methanol/air mixture. The MIT (minimum ignition temperature) and MIE (minimum ignition energy) are two important properties for designing safety standards and understanding the ignition process of combustible mixtures. The effects of the flame kernel size, flame kernel temperature and equivalence ratio were also examined on MIT, MIE and IDP (ignition delay period). The methanol mechanism was validated by experimental test. The simulated results showed that the flame kernel size, temperature and energy dramatically affected the values of the MIT, MIE and IDP for a methanol/air mixture, the value of the ignition delay period was not only related to the flame kernel energy, but also to the flame kernel temperature. - Highlights: • We used LES (large eddy simulation) coupled with detailed chemical kinetics to simulate methanol ignition. • The flame kernel size and temperature affected the minimum ignition temperature. • The flame kernel temperature and energy affected the ignition delay period. • The equivalence ratio of methanol–air mixture affected the ignition delay period

  19. Numerical simulation of premixed methane/air micro flame: Effects of simplified one step chemical kinetic mechanisms on the flame stability

    International Nuclear Information System (INIS)

    The effects of a simplified one step overall chemical kinetic equation on a micro flame were investigated with different kinetics models, namely Mantel, Duterque and the so called Arrhenius models. A numerical study of a premixed methane/air flame in lean conditions (ϕ = 0.9) within a rectangular tubular micro reactor was undertaken by solving the 2D governing equations. More precisely, their influence on the structure of the flame, the temperature of the fluid along the axial displacement of the reactor and the walls temperatures were analyzed. The results show that one step chemical kinetic mechanism affected both the shape of the flame and the combustion temperature whose magnitude is globally overestimated, corroborating the results in the existing literature. Among the three simulated models, the Mantel model allowed a stable flame anchored to the inlet reactor with a convex form, while the Duterque model gave a stable elongated flame with considerable ignition delay. A dead zone is observed with fluid accumulation at the entrance of the reactor which may explain the strong reaction rate and the very high combustion temperature obtained, despite the development of a flame in the form of a very hot illuminated spot lit all around. The so called Arrhenius model resulted in a rapid extinction of the flame and does not seem to take into account all the kinetic phenomena for appropriate numerical simulations of the micro combustion. Furthermore the one step overall chemical kinetic approach seems to determine the initial temperature applicable for both fluid flow area and the walls of the micro reactor that favors the inset of premixed mixture combustion during micro combustion calculations. - Highlights: • We simulate a methane/air micro flame with three single-step reaction models. • We analyze the interplay of simplified chemical kinetic mechanism on the flame structure. • The variation of the reaction zone causes blow out, flash back or hot spot

  20. 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.

  1. 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.

  2. 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...

  3. Parallelization of Kinetic Theory Simulations

    CERN Document Server

    Howell, Jim; Colbry, Dirk; Pickett, Rodney; Staber, Alec; Sagert, Irina; Strother, Terrance

    2013-01-01

    Numerical studies of shock waves in large scale systems via kinetic simulations with millions of particles are too computationally demanding to be processed in serial. In this work we focus on optimizing the parallel performance of a kinetic Monte Carlo code for astrophysical simulations such as core-collapse supernovae. Our goal is to attain a flexible program that scales well with the architecture of modern supercomputers. This approach requires a hybrid model of programming that combines a message passing interface (MPI) with a multithreading model (OpenMP) in C++. We report on our approach to implement the hybrid design into the kinetic code and show first results which demonstrate a significant gain in performance when many processors are applied.

  4. Chemical Transformation Simulator

    Science.gov (United States)

    The Chemical Transformation Simulator (CTS) is a web-based, high-throughput screening tool that automates the calculation and collection of physicochemical properties for an organic chemical of interest and its predicted products resulting from transformations in environmental sy...

  5. 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…

  6. 混合放电臭氧发生的反应动力学模拟%Chemical Kinetics Simulation of Ozone Production Using Multi-discharge

    Institute of Scientific and Technical Information of China (English)

    魏林生; 徐敏; 章亚芳; 胡兆吉

    2016-01-01

    A chemical kinetics model, which was established based on plasma Perfectly Stirred Reactor of CHEMKIN, was used to simulate chemical kinetics of ozone generation using multi-discharge and to analyze sensitivity and rate of production.The simulation results show that the prediction agrees well with experimental data, and the ozone concentration increases with decreasing gas pressure, inlet gas temperature and oxygen gas rate.Proper increase of specific energy is benefit for ozone generation, but excessive specific energy show opposite behavior.In terms of reaction pathway of ozone production, O, O(1D) and O2(b1∑) are the most important species for ozone generation.The fact that the specific energy can't be too high are verified and explained from microcosmic chemical kinetics view again, because the effect of major reaction for generating ozone precursor O atom E+O2=>O+O+E on ozone production decreases with increasing specific energy and temperature.In addition, the existences of O(1D), O2(b1∑) and excessive O are unfavorable for ozone generation.%为揭示混合放电臭氧高效发生机理,从反应动力学出发,采用CHEMKIN中Plasma PSR模块对混合放电臭氧发生的反应动力学进行了模拟,并作了敏感性分析和ROP分析,模拟结果与实验结果较相符.模拟结果表明气体压力、气体进口温度、气源流量的减小都有利于臭氧浓度的提高;比能的适当增加有利于臭氧的产生,过大则不利于臭氧合成.由反应路径图得到对臭氧合成的重要组分有O、O(1D)、O2(b1∑),并从微观动力学角度进一步验证和说明比能不能过大,因为臭氧前驱物氧原子的最主要途径E+O2=>O+O+E随着比能和温度的增加,其对臭氧合成的影响下降.另外O(1D)、O2(b1∑)以及过多的O的存在不利于臭氧的产生.

  7. Chemical Kinetics Simulation of Ozone Production Using Multi-discharge%混合放电臭氧发生的反应动力学模拟

    Institute of Scientific and Technical Information of China (English)

    魏林生; 徐敏; 章亚芳; 胡兆吉

    2016-01-01

    为揭示混合放电臭氧高效发生机理,从反应动力学出发,采用CHEMKIN中Plasma PSR模块对混合放电臭氧发生的反应动力学进行了模拟,并作了敏感性分析和ROP分析,模拟结果与实验结果较相符.模拟结果表明气体压力、气体进口温度、气源流量的减小都有利于臭氧浓度的提高;比能的适当增加有利于臭氧的产生,过大则不利于臭氧合成.由反应路径图得到对臭氧合成的重要组分有O、O(1D)、O2(b1∑),并从微观动力学角度进一步验证和说明比能不能过大,因为臭氧前驱物氧原子的最主要途径E+O2=>O+O+E随着比能和温度的增加,其对臭氧合成的影响下降.另外O(1D)、O2(b1∑)以及过多的O的存在不利于臭氧的产生.%A chemical kinetics model, which was established based on plasma Perfectly Stirred Reactor of CHEMKIN, was used to simulate chemical kinetics of ozone generation using multi-discharge and to analyze sensitivity and rate of production.The simulation results show that the prediction agrees well with experimental data, and the ozone concentration increases with decreasing gas pressure, inlet gas temperature and oxygen gas rate.Proper increase of specific energy is benefit for ozone generation, but excessive specific energy show opposite behavior.In terms of reaction pathway of ozone production, O, O(1D) and O2(b1∑) are the most important species for ozone generation.The fact that the specific energy can't be too high are verified and explained from microcosmic chemical kinetics view again, because the effect of major reaction for generating ozone precursor O atom E+O2=>O+O+E on ozone production decreases with increasing specific energy and temperature.In addition, the existences of O(1D), O2(b1∑) and excessive O are unfavorable for ozone generation.

  8. 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.

  9. 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

  10. 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

  11. 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.

  12. 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

  13. Kinetic distance and kinetic maps from molecular dynamics simulation

    CERN Document Server

    Noe, Frank

    2015-01-01

    Characterizing macromolecular kinetics from molecular dynamics (MD) simulations requires a distance metric that can distinguish slowly-interconverting states. Here we build upon diffusion map theory and define a kinetic distance for irreducible Markov processes that quantifies how slowly molecular conformations interconvert. The kinetic distance can be computed given a model that approximates the eigenvalues and eigenvectors (reaction coordinates) of the MD Markov operator. Here we employ the time-lagged independent component analysis (TICA). The TICA components can be scaled to provide a kinetic map in which the Euclidean distance corresponds to the kinetic distance. As a result, the question of how many TICA dimensions should be kept in a dimensionality reduction approach becomes obsolete, and one parameter less needs to be specified in the kinetic model construction. We demonstrate the approach using TICA and Markov state model (MSM) analyses for illustrative models, protein conformation dynamics in bovine...

  14. 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.

  15. 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...

  16. 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,…

  17. 多种复杂化学反应动力学统一的数值模拟%Numerical simulation for some kinds of complex chemical reaction kinetics

    Institute of Scientific and Technical Information of China (English)

    钟巍; 田宙

    2011-01-01

    研究各种经典复杂化学反应动力学方程如简单级次反应、平行反应、连续反应和对峙反应等的求解方法时,可以发现它们之间存在共同点,并得到统一的求解形式.文中给出了将多种复杂化学反应动力学的求解统一起来的方法,并用C++程序语言,编制了可以求解物理化学教学中各种经典复杂化学反应动力学方程的数值模拟程序.使用该程序,只要根据具体情况调整输入参数,就能解决不同的化学反应动力学问题.给出了求解连续反应和对峙反应的2个实例,验证了程序数值模拟的准确性.%The common points of all kinds of chemical kinetics were found by researching the classic chemical kinetics, such as n-order reaction, parallel reaction, consecutive reaction and opposing reaction, etc. And the different solutions of the chemical kinetics could be simplified as a general solution. The method to simplify the different solutions for complex chemical reaction kinetics was proposed, and a numerical simulation program to solve the equations by C++ programming language was presented. Inputting different parameters, the program can solve different chemical kinetics problems. Two examples of the consecutive reaction and the opposing reaction were given, by which the accuracy of the program in numerical simulation was verified.

  18. 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.

  19. Evaluation of reduced kinetics in simulation of gasified biomass gas combustion

    OpenAIRE

    ZHANG, Xiaoxiang; Jayasuriya, Jeevan; Fakhraie, Reza; Fransson, Torsten

    2013-01-01

    It is essentially important to use appropriate chemical kinetic models in the simulation process of gas turbine combustion. To integrate the detailed kinetics into complex combustion simulations has proven to be a computationally expensive task with tens to thousands of elementary reaction steps. It has been suggested that an appropriate simplified kinetics which are computationally efficient could be used instead. Therefore reduced kinetics are often used in CFD simulation of gas turbine com...

  20. 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.

  1. Kinetic distance and kinetic maps from molecular dynamics simulation.

    Science.gov (United States)

    Noé, Frank; Clementi, Cecilia

    2015-10-13

    Characterizing macromolecular kinetics from molecular dynamics (MD) simulations requires a distance metric that can distinguish slowly interconverting states. Here, we build upon diffusion map theory and define a kinetic distance metric for irreducible Markov processes that quantifies how slowly molecular conformations interconvert. The kinetic distance can be computed given a model that approximates the eigenvalues and eigenvectors (reaction coordinates) of the MD Markov operator. Here, we employ the time-lagged independent component analysis (TICA). The TICA components can be scaled to provide a kinetic map in which the Euclidean distance corresponds to the kinetic distance. As a result, the question of how many TICA dimensions should be kept in a dimensionality reduction approach becomes obsolete, and one parameter less needs to be specified in the kinetic model construction. We demonstrate the approach using TICA and Markov state model (MSM) analyses for illustrative models, protein conformation dynamics in bovine pancreatic trypsin inhibitor and protein-inhibitor association in trypsin and benzamidine. We find that the total kinetic variance (TKV) is an excellent indicator of model quality and can be used to rank different input feature sets. PMID:26574285

  2. Nonisothermal Analysis of Solution Kinetics by Spreadsheet Simulation

    Science.gov (United States)

    de Levie, Robert

    2012-01-01

    A fast and generally applicable alternative solution to the problem of determining the useful shelf life of medicinal solutions is described. It illustrates the power and convenience of the combination of numerical simulation and nonlinear least squares with a practical pharmaceutical application of chemical kinetics and thermodynamics, validated…

  3. A High Performance Chemical Simulation Preprocessor and Source Code Generator Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Numerical simulations of chemical kinetics are a critical component of aerospace research, Earth systems research, and energy research. These simulations enable a...

  4. Chemical simulation of greywater.

    Science.gov (United States)

    Abed, Suhail Najem; Scholz, Miklas

    2016-01-01

    Sustainable water resources management attracts considerable attention in today's world. Recycling and reuse of both wastewater and greywater are becoming more attractive. The strategy is to protect ecosystem services by balancing the withdrawal of water and the disposal of wastewater. In the present study, a timely and novel synthetic greywater composition has been proposed with respect to the composition of heavy metals, nutrients and organic matter. The change in water quality of the synthetic greywater due to increasing storage time was monitored to evaluate the stability of the proposed chemical formula. The new greywater is prepared artificially using analytical-grade chemicals to simulate either low (LC) or high (HC) pollutant concentrations. The characteristics of the synthetic greywater were tested (just before starting the experiment, after two days and a week of storage under real weather conditions) and compared to those reported for real greywater. Test results for both synthetic greywater types showed great similarities with the physiochemical properties of published findings concerning real greywater. Furthermore, the synthetic greywater is relatively stable in terms of its characteristics for different storage periods. However, there was a significant (p change was also noted for the reduction (70%) of nitrate-nitrogen (NO3-N) concerning HC greywater after seven days of storage. PMID:26745659

  5. 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.

  6. Extension of a Kinetic Approach to Chemical Reactions to Electronic Energy Levels and Reactions Involving Charged Species with Application to DSMC Simulations

    Science.gov (United States)

    Liechty, Derek S.

    2014-01-01

    The ability to compute rarefied, ionized hypersonic flows is becoming more important as missions such as Earth reentry, landing high mass payloads on Mars, and the exploration of the outer planets and their satellites are being considered. Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties are extended in the current work to include electronic energy level transitions and reactions involving charged particles. These extensions are shown to agree favorably with reported transition and reaction rates from the literature for near-equilibrium conditions. Also, the extensions are applied to the second flight of the Project FIRE flight experiment at 1634 seconds with a Knudsen number of 0.001 at an altitude of 76.4 km. In order to accomplish this, NASA's direct simulation Monte Carlo code DAC was rewritten to include the ability to simulate charge-neutral ionized flows, take advantage of the recently introduced chemistry model, and to include the extensions presented in this work. The 1634 second data point was chosen for comparisons to be made in order to include a CFD solution. The Knudsen number at this point in time is such that the DSMC simulations are still tractable and the CFD computations are at the edge of what is considered valid because, although near-transitional, the flow is still considered to be continuum. It is shown that the inclusion of electronic energy levels in the DSMC simulation is necessary for flows of this nature and is required for comparison to the CFD solution. The flow field solutions are also post-processed by the nonequilibrium radiation code HARA to compute the radiative portion.

  7. Lattice kinetic simulation of nonisothermal magnetohydrodynamics.

    Science.gov (United States)

    Chatterjee, Dipankar; Amiroudine, Sakir

    2010-06-01

    In this paper, a lattice kinetic algorithm is presented to simulate nonisothermal magnetohydrodynamics in the low-Mach number incompressible limit. The flow and thermal fields are described by two separate distribution functions through respective scalar kinetic equations and the magnetic field is governed by a vector distribution function through a vector kinetic equation. The distribution functions are only coupled via the macroscopic density, momentum, magnetic field, and temperature computed at the lattice points. The novelty of the work is the computation of the thermal field in conjunction with the hydromagnetic fields in the lattice Boltzmann framework. A 9-bit two-dimensional (2D) lattice scheme is used for the numerical computation of the hydrodynamic and thermal fields, whereas the magnetic field is simulated in a 5-bit 2D lattice. Simulation of Hartmann flow in a channel provides excellent agreement with corresponding analytical results. PMID:20866540

  8. Kinetic Monte Carlo simulation of dislocation dynamics

    International Nuclear Information System (INIS)

    A kinetic Monte Carlo simulation of dislocation motion is introduced. The dislocations are assumed to be composed of pure edge and screw segments confined to a fixed lattice. The stress and temperature dependence of the dislocation velocity is studied, and finite-size effects are discussed. It is argued that surfaces and boundaries may play a significant role in the velocity of dislocations. The simulated dislocations are shown to display kinetic roughening according to the exponents predicted by the Kardar-Parisi-Zhang equation. copyright 1999 The American Physical Society

  9. 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

  10. Simulations of chemical catalysis

    Science.gov (United States)

    Smith, Gregory K.

    This dissertation contains simulations of chemical catalysis in both biological and heterogeneous contexts. A mixture of classical, quantum, and hybrid techniques are applied to explore the energy profiles and compare possible chemical mechanisms both within the context of human and bacterial enzymes, as well as exploring surface reactions on a metal catalyst. A brief summary of each project follows. Project 1 - Bacterial Enzyme SpvC The newly discovered SpvC effector protein from Salmonella typhimurium interferes with the host immune response by dephosphorylating mitogen-activated protein kinases (MAPKs) with a beta-elimination mechanism. The dynamics of the enzyme substrate complex of the SpvC effector is investigated with a 3.2 ns molecular dynamics simulation, which reveals that the phosphorylated peptide substrate is tightly held in the active site by a hydrogen bond network and the lysine general base is positioned for the abstraction of the alpha hydrogen. The catalysis is further modeled with density functional theory (DFT) in a truncated active-site model at the B3LYP/6-31 G(d,p) level of theory. The truncated model suggested the reaction proceeds via a single transition state. After including the enzyme environment in ab initio QM/MM studies, it was found to proceed via an E1cB-like pathway, in which the carbanion intermediate is stabilized by an enzyme oxyanion hole provided by Lys104 and Tyr158 of SpvC. Project 2 - Human Enzyme CDK2 Phosphorylation reactions catalyzed by kinases and phosphatases play an indispensable role in cellular signaling, and their malfunctioning is implicated in many diseases. Ab initio quantum mechanical/molecular mechanical studies are reported for the phosphoryl transfer reaction catalyzed by a cyclin-dependent kinase, CDK2. Our results suggest that an active-site Asp residue, rather than ATP as previously proposed, serves as the general base to activate the Ser nucleophile. The corresponding transition state features a

  11. 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.

  12. Simulations of kinetically irreversible protein aggregate structure.

    OpenAIRE

    Patro, S Y; Przybycien, T M

    1994-01-01

    We have simulated the structure of kinetically irreversible protein aggregates in two-dimensional space using a lattice-based Monte-Carlo routine. Our model specifically accounts for the intermolecular interactions between hydrophobic and hydrophilic protein surfaces and a polar solvent. The simulations provide information about the aggregate density, the types of inter-monomer contacts and solvent content within the aggregates, the type and extent of solvent exposed perimeter, and the short-...

  13. 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.

  14. 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.

  15. 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).

  16. 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.

  17. Kinetic Vlasov simulations of collisionless magnetic reconnection

    Science.gov (United States)

    Schmitz, H.; Grauer, R.

    2006-09-01

    A fully kinetic Vlasov simulation of the Geospace Environment Modeling Magnetic Reconnection Challenge is presented. Good agreement is found with previous kinetic simulations using particle in cell (PIC) codes, confirming both the PIC and the Vlasov code. In the latter the complete distribution functions fk (k=i,e) are discretized on a numerical grid in phase space. In contrast to PIC simulations, the Vlasov code does not suffer from numerical noise and allows a more detailed investigation of the distribution functions. The role of the different contributions of Ohm's law are compared by calculating each of the terms from the moments of the fk. The important role of the off-diagonal elements of the electron pressure tensor could be confirmed. The inductive electric field at the X line is found to be dominated by the nongyrotropic electron pressure, while the bulk electron inertia is of minor importance. Detailed analysis of the electron distribution function within the diffusion region reveals the kinetic origin of the nongyrotropic terms.

  18. 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

  19. Kinetic Vlasov Simulations of collisionless magnetic Reconnection

    CERN Document Server

    Schmitz, H

    2006-01-01

    A fully kinetic Vlasov simulation of the Geospace Environment Modeling (GEM) Magnetic Reconnection Challenge is presented. Good agreement is found with previous kinetic simulations using particle in cell (PIC) codes, confirming both the PIC and the Vlasov code. In the latter the complete distribution functions $f_k$ ($k=i,e$) are discretised on a numerical grid in phase space. In contrast to PIC simulations, the Vlasov code does not suffer from numerical noise and allows a more detailed investigation of the distribution functions. The role of the different contributions of Ohm's law are compared by calculating each of the terms from the moments of the $f_k$. The important role of the off--diagonal elements of the electron pressure tensor could be confirmed. The inductive electric field at the X--Line is found to be dominated by the non--gyrotropic electron pressure, while the bulk electron inertia is of minor importance. Detailed analysis of the electron distribution function within the diffusion region revea...

  20. Kinetic energy of rainfall simulation nozzles

    Science.gov (United States)

    Different spray nozzles are used frequently to simulate natural rain for soil erosion and chemical transport, particularly phosphorous (P), studies. Oscillating VeeJet nozzles are used mostly in soil erosion research while constant spray FullJet nozzles are commonly used for P transport. Several ch...

  1. 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…

  2. Kinetic simulations in plasmas: a general view and some applications

    International Nuclear Information System (INIS)

    In these lecture notes we talk about kinetic simulations plasma physics. We present a general view of the different approach that can be given to kinetic plasmas depending on the physical problem to be investigated. Some applications of kinetic simulations to space plasma phenomena and Pierce electrodes are introduced. (author)

  3. 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.

  4. Personal Simulator of Chemical Process

    Institute of Scientific and Technical Information of China (English)

    吴重光

    2002-01-01

    The Personal Simulator of chemical process (PS) means that fully simulationsoftware can be run on one personal computer. This paper describes the kinds of PSprograms, its features, the graphic functions and three examples. PS programs are allbased on one object-oriented and real-time simulation software environment. Authordevelops this simulation software environment. An example of the batch reaction kineticsmodel is also described. Up to now a lot of students in technical schools and universitieshave trained on PS. The training results are very successful.

  5. 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.

  6. Kinetic Simulations of Dense Plasma Focus Breakdown

    Science.gov (United States)

    Schmidt, A.; Higginson, D. P.; Jiang, S.; Link, A.; Povilus, A.; Sears, J.; Bennett, N.; Rose, D. V.; Welch, D. R.

    2015-11-01

    A dense plasma focus (DPF) device is a type of plasma gun that drives current through a set of coaxial electrodes to assemble gas inside the device and then implode that gas on axis to form a Z-pinch. This implosion drives hydrodynamic and kinetic instabilities that generate strong electric fields, which produces a short intense pulse of x-rays, high-energy (>100 keV) electrons and ions, and (in deuterium gas) neutrons. A strong factor in pinch performance is the initial breakdown and ionization of the gas along the insulator surface separating the two electrodes. The smoothness and isotropy of this ionized sheath are imprinted on the current sheath that travels along the electrodes, thus making it an important portion of the DPF to both understand and optimize. Here we use kinetic simulations in the Particle-in-cell code LSP to model the breakdown. Simulations are initiated with neutral gas and the breakdown modeled self-consistently as driven by a charged capacitor system. We also investigate novel geometries for the insulator and electrodes to attempt to control the electric field profile. The initial ionization fraction of gas is explored computationally to gauge possible advantages of pre-ionization which could be created experimentally via lasers or a glow-discharge. Prepared by LLNL under Contract DE-AC52-07NA27344.

  7. 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.

  8. Lanczos and Recursion Techniques for Multiscale Kinetic Monte Carlo Simulations

    Energy Technology Data Exchange (ETDEWEB)

    Rudd, R E; Mason, D R; Sutton, A P

    2006-03-13

    We review an approach to the simulation of the class of microstructural and morphological evolution involving both relatively short-ranged chemical and interfacial interactions and long-ranged elastic interactions. The calculation of the anharmonic elastic energy is facilitated with Lanczos recursion. The elastic energy changes affect the rate of vacancy hopping, and hence the rate of microstructural evolution due to vacancy mediated diffusion. The elastically informed hopping rates are used to construct the event catalog for kinetic Monte Carlo simulation. The simulation is accelerated using a second order residence time algorithm. The effect of elasticity on the microstructural development has been assessed. This article is related to a talk given in honor of David Pettifor at the DGP60 Workshop in Oxford.

  9. 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

  10. 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.

  11. 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...

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

    Science.gov (United States)

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

    1990-01-01

    Numerical solutions of the Jet-A spray combustion were obtained by means of the KIVA-II computer code after Jet-A properties were added to the 12 chemical species the program had initially contained. Three different reaction mechanism models are considered. The first model consists of 131 reactions and 45 species; it is evaluated by comparing calculated ignition delay times with available shock tube data, and it is used in the evaluation of the other two simplified models. The simplified mechanisms consider 45 reactions and 27 species and 5 reactions and 12 species, respectively. In the prediction of pollutants NOx and CO, the full mechanism of 131 reactions is considered to be more reliable. The numerical results indicate that the variation of the maximum flame temperature is within 20 percent as compared with that of the full mechanism of 131 reactions. The chemical compositions of major components such as C3H8, H2O, O2, CO2, and N2 are of the same order of magnitude. However, the concentrations of pollutants are quite different.

  13. 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…

  14. 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.

  15. Efficient procedures for the numerical simulation of mid-size RNA kinetics

    OpenAIRE

    Aviram, Iddo; Veltman, Ilia; Churkin, Alexander; Barash, Danny

    2012-01-01

    Motivation Methods for simulating the kinetic folding of RNAs by numerically solving the chemical master equation have been developed since the late 90's, notably the programs Kinfold and Treekin with Barriers that are available in the Vienna RNA package. Our goal is to formulate extensions to the algorithms used, starting from the Gillespie algorithm, that will allow numerical simulations of mid-size (~ 60–150 nt) RNA kinetics in some practical cases where numerous distributions of folding t...

  16. Efficient procedures for the numerical simulation of mid-size RNA kinetics

    OpenAIRE

    Aviram Iddo; Veltman Ilia; Churkin Alexander; Barash Danny

    2012-01-01

    Abstract Motivation Methods for simulating the kinetic folding of RNAs by numerically solving the chemical master equation have been developed since the late 90's, notably the programs Kinfold and Treekin with Barriers that are available in the Vienna RNA package. Our goal is to formulate extensions to the algorithms used, starting from the Gillespie algorithm, that will allow numerical simulations of mid-size (~ 60–150 nt) RNA kinetics in some practical cases where numerous distributions of ...

  17. 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.

  18. 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.

  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. Aerosol kinetic code "AERFORM": Model, validation and simulation results

    Science.gov (United States)

    Gainullin, K. G.; Golubev, A. I.; Petrov, A. M.; Piskunov, V. N.

    2016-06-01

    The aerosol kinetic code "AERFORM" is modified to simulate droplet and ice particle formation in mixed clouds. The splitting method is used to calculate condensation and coagulation simultaneously. The method is calibrated with analytic solutions of kinetic equations. Condensation kinetic model is based on cloud particle growth equation, mass and heat balance equations. The coagulation kinetic model includes Brownian, turbulent and precipitation effects. The real values are used for condensation and coagulation growth of water droplets and ice particles. The model and the simulation results for two full-scale cloud experiments are presented. The simulation model and code may be used autonomously or as an element of another code.

  1. 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

  2. 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.

  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. 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...

  5. Kinetic model of continuous-wave flow chemical lasers

    Science.gov (United States)

    Gao, Z.; X., E.

    1982-02-01

    A kinetic approach to modeling the gain in a chemical wave continuous laser when the lasing frequency is coincident with the center of the line shape is presented. Governing equations are defined for the relaxing behavior of an initially nonequilibrium distribution toward the local equilibrium Boltzmann-Maxwellian distribution. A new gain is introduced which is related to the thermal motion of the molecules and cold-reaction and premixed CW models are discussed. Coincidence of the lasing frequency with the line shape is demonstrated to result in a radiative intensity within the homogeneous broadening limit. The rate model predictions are compared with those of the kinetic model. It is found that when the broadening parameter is less than 0.2 the kinetic model more accurately describes the behavior of the CW chemical laser.

  6. Cometary impact and amino acid survival - Chemical kinetics and thermochemistry

    Science.gov (United States)

    Ross, D.S.

    2006-01-01

    The Arrhenius parameters for the initiating reactions in butane thermolysis and the formation of soot, reliable to at least 3000 K, have been applied to the question of the survival of amino acids in cometary impacts on early Earth. The pressure/temperature/time course employed here was that developed in hydrocode simulations for kilometer-sized comets (Pierazzo and Chyba, 1999), with attention to the track below 3000 K where it is shown that potential stabilizing effects of high pressure become unimportant kinetically. The question of survival can then be considered without the need for assignment of activation volumes and the related uncertainties in their application to extreme conditions. The exercise shows that the characteristic times for soot formation in the interval fall well below the cooling periods for impacts ranging from fully vertical down to about 9?? above horizontal. Decarboxylation, which emerges as more rapid than soot formation below 2000-3000 K, continues further down to extremely narrow impact angles, and accordingly cometa??ry delivery of amino acids to early Earth is highly unlikely. ?? 2006 American Chemical Society.

  7. 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…

  8. 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...

  9. QUIC: a chemical kinetics code for use with the chemical equilibrium code QUIL

    International Nuclear Information System (INIS)

    A chemical rate kinetics code QUIC is described, along with a support code RATE. QUIC is designed to allow chemical kinetics calculations on a wide variety of chemical environments while operating in the overlay environment of the chemical equilibrium code QUIL. QUIC depends upon a rate-data library called LIBR. This library is maintained by RATE. RATE enters into the library all reactions in a standardized format. The code QUIC, operating in conjunction with QUIL, is interactive and written to be used from a remote terminal, with paging control provided. Plotted output is also available

  10. 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.

  11. 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.

  12. 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.

  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. 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.

  15. Numerical Simulation of Fixed-Bed Catalytic Reforming Reactors: Hydrodynamics / Chemical Kinetics Coupling Simulation numérique des réacteurs de reformage catalytique en lit fixe : couplage hydrodynamique-cinétique chimique

    Directory of Open Access Journals (Sweden)

    Ferschneider G.

    2006-11-01

    Full Text Available Fixed bed reactors with a single fluid phase are widely used in the refining or petrochemical industries for reaction processes catalysed by a solid phase. The design criteria for industrial reactors are relatively well known. However, they rely on a one-dimensional writing and on the separate resolution of the equation of conservation of mass and energy, and of momentum. Thus, with complex geometries, the influence of hydrodynamics on the effectiveness of the catalyst bed cannot be taken into account. The calculation method proposed is based on the multi-dimensional writing and the simultaneous resolution of the local conservation equations. The example discussed concerns fixed-bed catalytic reactors. These reactors are distinguished by their annular geometry and the radial circulation of the feedstock. The flow is assumed to be axisymmetric. The reaction process is reflected by a simplified kinetic mechanism involving ten chemical species. Calculation of the hydrodynamic (mean velocities, pressure, thermal and mass fields (concentration of each species serves to identify the influence of internal components in two industrial reactor geometries. The map of the quantity of coke formed and deposited on the catalyst, calculated by the model, reveals potential areas of poor operation. Les réacteurs à lit fixe avec une seule phase fluide sont largement utilisés dans l'industrie du raffinage et de la pétrochimie, pour mettre en oeuvre un processus réactionnel catalysé par une phase solide. Les règles de conception des réacteurs industriels sont relativement bien connues. Cependant, elles reposent sur l'écriture monodimensionnelle et la résolution séparée, d'une part, des équations de conservation de la masse et de l'énergie et d'autre part, de la quantité de mouvement. Ainsi dans le cas de géométries complexes, l'influence de l'hydrodynamique sur l'efficacité du lit catalytique ne peut être prise en compte. La méthode de calcul

  16. 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.

  17. 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

  18. Hypocoercivity in metastable settings and kinetic simulated annealing

    OpenAIRE

    Monmarché, Pierre

    2015-01-01

    Classical analysis of the simulated annealing algorithm is combined with the more recent hypocoercive method of distorted entropy to prove the convergence for large time of the kinetic Langevin annealing with logarithmic cooling schedule.

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

    OpenAIRE

    Feliu, Elisenda; Wiuf, Carsten

    2011-01-01

    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 of variables. The procedure reduces the variables in the system to a set of "core" variables by eliminating variables corresponding to a set of non-interacting species. The steady states are paramet...

  20. Chemical Kinetic Models for HCCI and Diesel Combustion

    Energy Technology Data Exchange (ETDEWEB)

    Pitz, W J; Westbook, C K; Mehl, M

    2008-10-30

    Hydrocarbon fuels for advanced combustion engines consist of complex mixtures of hundreds or even thousands of different components. These components can be grouped into a number of chemically distinct classes, consisting of n-paraffins, branched paraffins, cyclic paraffins, olefins, oxygenates, and aromatics. Biodiesel contains its own unique chemical class called methyl esters. The fractional amounts of these chemical classes are quite different in gasoline, diesel fuel, oil-sand derived fuels and bio-derived fuels, which contributes to the very different combustion characteristics of each of these types of combustion systems. The objectives of this project are: (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.

  1. 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.

  2. 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.

  3. Introducing Michaelis-Menten Kinetics through Simulation

    Science.gov (United States)

    Halkides, Christopher J.; Herman, Russell

    2007-01-01

    We describe a computer tutorial that introduces the concept of the steady state in enzyme kinetics. The tutorial allows students to produce graphs of the concentrations of free enzyme, enzyme-substrate complex, and product versus time in order to learn about the approach to steady state. By using a range of substrate concentrations and rate…

  4. 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...

  5. Consistent interpretation of molecular simulation kinetics using Markov state models biased with external information

    CERN Document Server

    Rudzinski, Joseph F; Bereau, Tristan

    2016-01-01

    Molecular simulations can provide microscopic insight into the physical and chemical driving forces of complex molecular processes. Despite continued advancement of simulation methodology, model errors may lead to inconsistencies between simulated and reference (e.g., from experiments or higher-level simulations) observables. To bound the microscopic information generated by computer simulations within reference measurements, we propose a method that reweights the microscopic transitions of the system to improve consistency with a set of coarse kinetic observables. The method employs the well-developed Markov state modeling framework to efficiently link microscopic dynamics with long-time scale constraints, thereby consistently addressing a wide range of time scales. To emphasize the robustness of the method, we consider two distinct coarse-grained models with significant kinetic inconsistencies. When applied to the simulated conformational dynamics of small peptides, the reweighting procedure systematically ...

  6. 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.

  7. A nondissipative simulation method for the drift kinetic equation

    Energy Technology Data Exchange (ETDEWEB)

    Watanabe, Tomo-Hiko; Sugama, Hideo; Sato, Tetsuya

    2001-07-01

    With the aim to study the ion temperature gradient (ITG) driven turbulence, a nondissipative kinetic simulation scheme is developed and comprehensively benchmarked. The new simulation method preserving the time-reversibility of basic kinetic equations can successfully reproduce the analytical solutions of asymmetric three-mode ITG equations which are extended to provide a more general reference for benchmarking than the previous work [T.-H. Watanabe, H. Sugama, and T. Sato: Phys. Plasmas 7 (2000) 984]. It is also applied to a dissipative three-mode system, and shows a good agreement with the analytical solution. The nondissipative simulation result of the ITG turbulence accurately satisfies the entropy balance equation. Usefulness of the nondissipative method for the drift kinetic simulations is confirmed in comparisons with other dissipative schemes. (author)

  8. Accuracy and precision of protein–ligand interaction kinetics determined from chemical shift titrations

    International Nuclear Information System (INIS)

    NMR-monitored chemical shift titrations for the study of weak protein–ligand interactions represent a rich source of information regarding thermodynamic parameters such as dissociation constants (KD) in the micro- to millimolar range, populations for the free and ligand-bound states, and the kinetics of interconversion between states, which are typically within the fast exchange regime on the NMR timescale. We recently developed two chemical shift titration methods wherein co-variation of the total protein and ligand concentrations gives increased precision for the KD value of a 1:1 protein–ligand interaction (Markin and Spyracopoulos in J Biomol NMR 53: 125–138, 2012). In this study, we demonstrate that classical line shape analysis applied to a single set of 1H–15N 2D HSQC NMR spectra acquired using precise protein–ligand chemical shift titration methods we developed, produces accurate and precise kinetic parameters such as the off-rate (koff). For experimentally determined kinetics in the fast exchange regime on the NMR timescale, koff ∼ 3,000 s−1 in this work, the accuracy of classical line shape analysis was determined to be better than 5 % by conducting quantum mechanical NMR simulations of the chemical shift titration methods with the magnetic resonance toolkit GAMMA. Using Monte Carlo simulations, the experimental precision for koff from line shape analysis of NMR spectra was determined to be 13 %, in agreement with the theoretical precision of 12 % from line shape analysis of the GAMMA simulations in the presence of noise and protein concentration errors. In addition, GAMMA simulations were employed to demonstrate that line shape analysis has the potential to provide reasonably accurate and precise koff values over a wide range, from 100 to 15,000 s−1. The validity of line shape analysis for koff values approaching intermediate exchange (∼100 s−1), may be facilitated by more accurate KD measurements from NMR-monitored chemical shift

  9. 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.

  10. Plasma simulation with parallel kinetic particle codes

    Czech Academy of Sciences Publication Activity Database

    Gibbon, P.; Speck, R.; Berberich, B.; Karmakar, A.; Arnold, L.; Mašek, Martin

    Jülich : Forschungszentrum Jülich GmbH, 2010 - (Münster, G.; Wolf, D.; Kremer, M.), 383 - 390 ISBN 978-3-89336-606-4. - (IAS Series. vol. 3). [ NIC Symposium 2010. Jülich (DE), 24.02.2010-25.02.2010] Institutional research plan: CEZ:AV0Z10100523 Keywords : x-ray sources * ion acceleration * parallel kinetic particle codes * mesh-free tree code * Darwin model Subject RIV: BL - Plasma and Gas Discharge Physics http://www.fz-juelich.de/ias/datapool/page/12/gibbon.pdf

  11. Kinetic Simulations of Ladder Climbing and Autoresonance of Plasma Waves

    Science.gov (United States)

    Kaminski, Erez; Barth, Ido; Fisch, Nat; Dodin, Ilya

    2015-11-01

    Quantum like Ladder Climbing and Autoresonance of classical Langmuir waves in bounded plasmas are numerically studied within a kinetic model and compared with earlier fluid model simulations. Both dynamical solutions are excited and controlled via chirped modulations of the background density that preserve the plasma wave quanta. Landau damping determines the system's maximal stable level, imposing a kinetic limit on the maximal level of the Ladder Climbing or Autoresonance dynamics. Vlasov simulations are employed to test the kinetic stability of both dynamics and to find the kinetic limit for different system's parameters. This work was Supported by NNSA grant DE274-FG52-08NA28553, DOE contract DE-AC02-09CH11466, and DTRA grant HDTRA1-11-1-0037.

  12. 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.

  13. 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.

  14. 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...

  15. Kinetic transport simulation of energetic particles

    Science.gov (United States)

    Sheng, He; Waltz, R. E.

    2016-05-01

    A kinetic transport code (EPtran) is developed for the transport of the energetic particles (EPs). The EPtran code evolves the EP distribution function in radius, energy, and pitch angle phase space (r, E, λ) to steady state with classical slowing down, pitch angle scattering, as well as radial and energy transport of the injected EPs (neutral beam injection (NBI) or fusion alpha). The EPtran code is illustrated by treating the transport of NBI fast ions from high-n ITG/TEM micro-turbulence and EP driven unstable low-n Alfvén eigenmodes (AEs) in a well-studied DIII-D NBI heated discharge with significant AE central core loss. The kinetic transport code results for this discharge are compared with previous study using a simple EP density moment transport code ALPHA (R.E. Waltz and E.M. Bass 2014 Nucl. Fusion 54 104006). The dominant EP-AE transport is treated with a local stiff critical EP density (or equivalent pressure) gradient radial transport model modified to include energy-dependence and the nonlocal effects EP drift orbits. All previous EP transport models assume that the EP velocity space distribution function is not significantly distorted from the classical ‘no transport’ slowing down distribution. Important transport distortions away from the slowing down EP spectrum are illustrated by a focus on the coefficient of convection: EP energy flux divided by the product of EP average energy and EP particle flux.

  16. 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.

  17. Kinetics of chemical interactions between zirconium alloys and stainless steels

    International Nuclear Information System (INIS)

    The chemical interaction kinetics of reactor core component zirconium alloys and stainless steels at high temperatures was examined. Interaction of as-received and preoxidized Zr1%Nb with X18H10T stainless steel used in WWER type nuclear reactors, and also that of Zircaloy-4 and AISI-316 stainless steel, for comparison, were investigated. The reaction rate measurements were supplemented with post-test metallographical examinations. Results are presented and evaluated, and compared with literature data. (author). 14 refs., 31 figs., 8 tabs

  18. 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.

  19. Simulation of the Kinetics of Growth of Iron Nanoparticles in the Process of Chemical Vapor Deposition of Hydrocarbons with Injection of Ferrocene for the Synthesis of Carbon-Nanotube Arrays

    Science.gov (United States)

    Futko, S. I.; Shulitskii, B. G.; Labunov, V. A.; Ermolaeva, E. M.

    2015-11-01

    A kinetic model of growth of iron nanoparticles in the process of synthesis of carbon-nanotube arrays in an injection-type reactor of chemical vapor deposition, in which iron nanoparticles are formed as a result of the coalescence of iron atoms representing products of the thermal decomposition of a mixture of ferrocene with xylene, has been developed. It is shown that the formation of iron nanoparticles in the indicated reactor is very nonequilibrium in character. The parametric dependences of the monodisperse distributions of iron nanoparticles by their diameter, number density, and volume fraction on the flow rate of nitrogen, the temperature of the high-temperature region in the reactor, and the concentration of ferrocene in xylene have been obtained. The calculations performed have shown that the diameter of the iron nanoparticles formed increases monotonically with increase in the temperature of the chemical vapor deposition of hydrocarbons and the concentration of ferrocene in xylene and, quite the reverse, decreases monotonically with increase in the rate of the nitrogen flow. The calculated and experimental diameters of the iron nanoparticles formed at mass fractions of ferrocene in xylene of 0.5-10% were compared. The model proposed can be used for calculating the synthesis of carbon nanotubes in a chemical-vapor-deposition reactor of the injection type.

  20. 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...

  1. Double-focusing mixing jet for XFEL study of chemical kinetics

    International Nuclear Information System (INIS)

    A novel method for time-resolved study of chemical kinetics using a windowless mixing jet at an X-ray free-electron laser (XFEL) is described and demonstrated. The short mixing time gives a time resolution of about 250 µs; the design introduces controllable delays after the initiation of a chemical reaction, allowing the possibility for detection of transient structures by an XFEL beam pulse. Applications may include time-resolved enzyme–substrate imaging or protein folding. Several liquid sample injection methods have been developed to satisfy the requirements for serial femtosecond X-ray nanocrystallography, which enables radiation-damage-free determination of molecular structure at room temperature. Time-resolved nanocrystallography would combine structure analysis with chemical kinetics by determining the structures of the transient states and chemical kinetic mechanisms simultaneously. A windowless liquid mixing jet device has been designed for this purpose. It achieves fast uniform mixing of substrates and enzymes in the jet within 250 µs, with an adjustable delay between mixing and probing by the X-ray free-electron laser beam of up to 1 s for each frame of a ‘movie’. The principle of the liquid mixing jet device is illustrated using numerical simulation, and experimental results are presented using a fluorescent dye

  2. Detailed Chemical Kinetic Mechanisms for Combustion of Oxygenated Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Fisher, E.M.; Pitz, W.J.; Curran, H.J.; Westbrook, C.K.

    2000-01-11

    Thermodynamic properties and detailed chemical kinetic models have been developed for the combustion of two oxygenates: methyl butanoate, a model compound for biodiesel fuels, and methyl formate, a related simpler molecule. Bond additivity methods and rules for estimating kinetic parameters were adopted from hydrocarbon combustion and extended. The resulting mechanisms have been tested against the limited combustion data available in the literature, which was obtained at low temperature, subatmospheric conditions in closed vessels, using pressure measurements as the main diagnostic. Some qualitative agreement was obtained, but the experimental data consistently indicated lower overall reactivities than the model, differing by factors of 10 to 50. This discrepancy, which occurs for species with well-established kinetic mechanisms as well as for methyl esters, is tentatively ascribed to the presence of wall reactions in the experiments. The model predicts a region of weak or negative dependence of overall reaction rate on temperature for each methyl ester. Examination of the reaction fluxes provides an explanation of this behavior, involving a temperature-dependent competition between chain-propagating unimolecular decomposition processes and chain-branching processes, similar to that accepted for hydrocarbons. There is an urgent need to obtain more complete experimental data under well-characterized conditions for thorough testing of the model.

  3. 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

  4. Kinetic Simulations of Rayleigh-Taylor Instabilities

    OpenAIRE

    Sagert, Irina; Bauer, Wolfgang; Colbry, Dirk; Howell, Jim; Staber, Alec; Strother, Terrance

    2014-01-01

    We report on an ongoing project to develop a large scale Direct Simulation Monte Carlo code. The code is primarily aimed towards applications in astrophysics such as simulations of core-collapse supernovae. It has been tested on shock wave phenomena in the continuum limit and for matter out of equilibrium. In the current work we focus on the study of fluid instabilities. Like shock waves these are routinely used as test-cases for hydrodynamic codes and are discussed to play an important role ...

  5. Thermodynamics and kinetics of apoazurin folding under macromolecular crowding effect and chemical interference

    Science.gov (United States)

    Zegarra, Fabio; Cheung, Margaret

    2013-03-01

    Proteins fold in a cellular milieu crowded by different kinds of macromolecules. They exert volume exclusion impacting protein folding processes in vivo. Folding processes, however, has been studied by chemical denaturation under in vitro conditions. The impact of the two factors as an attempt to advance the understanding of folding mechanism in vivo is not understood. Here, we investigate the folding mechanisms of apoazurin affected by the macromolecular crowding and chemical interference by using coarse-grained molecular simulations. Crowding agents are modeled as hard-spheres and the chemical denaturation effects are implemented into an energy function of the side chain and backbone interactions. Protein folding stability, mechanism, and kinetics rates of apoazurin under chemical interference and macromolecular crowding conditions are being investigated. Supported by NSF, Molecular & Cellular Biosciences (MCB0919974).

  6. Issues in Kinetic Edge Turbulence Simulation

    Science.gov (United States)

    Parker, S. E.; Chen, Y.; Lang, J.

    2006-10-01

    Simulations of trapped electron modes are underway using GEM [1,2], a global electromagnetic gyrokinetic delta-f simulation with collisions. We report results with no temperature gradient so that ITG and ETG instabilities are not present. For typical weak density gradient core values, the CTEM is dominant. However, for steeper density gradient edge values, higher k drift-waves are most unstable [J. Lang this mtg.]. For the weaker density gradient core case, nonlinear simulations using GEM are routine. For the steeper gradient edge case, the nonlinear fluctuations are very high and a stationary state has not been obtained. More physics, e.g. profile variation and equilibrium ExB shear flow should be significantly stabilizing, and may make such simulations feasible using standard delta-f techniques. These features are fully implemented in GEM and research is ongoing. One approach to addressing the high fluctuation levels in the edge turbulence regime is the particle-continuum method [3]. A new scheme that periodically resets the particle weights, using a Maxwellian particle load is being tested in GEM [Y. Chen this mtg.] and will be discussed. [1] Y. Chen, S. Parker, J. Comput. Phys. 189 463 (2003). [2] Y. Chen, S. Parker, accepted, available on-line, J. Comput. Phys. (2006). [4] S. Vadlamani, S. Parker, Y. Chen and C. Kim, Comput. Phys. Comm. 164 209 (2004).

  7. Accelerated Stochastic Simulation of Large Chemical Systems

    Institute of Scientific and Technical Information of China (English)

    CHEN Xiao; AO Ling

    2007-01-01

    For efficient simulation of chemical systems with large number of reactions, we report a fast and exact algorithm for direct simulation of chemical discrete Markov processes. The approach adopts the scheme of organizing the reactions into hierarchical groups. By generating a random number, the selection of the next reaction that actually occurs is accomplished by a few successive selections in the hierarchical groups. The algorithm which is suited for simulating systems with large number of reactions is much faster than the direct method or the optimized direct method. For a demonstration of its efficiency, the accelerated algorithm is applied to simulate the reaction-diffusion Brusselator model on a discretized space.

  8. Kinetic Simulations of Rayleigh-Taylor Instabilities

    Science.gov (United States)

    Sagert, Irina; Bauer, Wolfgang; Colbry, Dirk; Howell, Jim; Staber, Alec; Strother, Terrance

    2014-09-01

    We report on an ongoing project to develop a large scale Direct Simulation Monte Carlo code. The code is primarily aimed towards applications in astrophysics such as simulations of core-collapse supernovae. It has been tested on shock wave phenomena in the continuum limit and for matter out of equilibrium. In the current work we focus on the study of fluid instabilities. Like shock waves these are routinely used as test-cases for hydrodynamic codes and are discussed to play an important role in the explosion mechanism of core-collapse supernovae. As a first test we study the evolution of a single-mode Rayleigh-Taylor instability at the interface of a light and a heavy fluid in the presence of a gravitational acceleration. To suppress small-wavelength instabilities caused by the irregularity in the separation layer we use a large particle mean free path. The latter leads to the development of a diffusion layer as particles propagate from one fluid into the other. For small amplitudes, when the instability is in the linear regime, we compare its position and shape to the analytic prediction. Despite the broadening of the fluid interface we see a good agreement with the analytic solution. At later times we observe the development of a mushroom like shape caused by secondary Kelvin-Helmholtz instabilities as seen in hydrodynamic simulations and consistent with experimental observations.

  9. Solar-simulator-pumped atomic iodine laser kinetics

    Science.gov (United States)

    Wilson, H. W.; Raju, S.; Shiu, Y. J.

    1983-01-01

    The literature contains broad ranges of disagreement in kinetic data for the atomic iodine laser. A kinetic model of a solar-simulator-pumped iodine laser is used to select those kinetic data consistent with recent laser experiments at the Langley Research Center. Analysis of the solar-simulator-pumped laser experiments resulted in the following estimates of rate coefficients: for alkyl radical (n-C3F7) and atomic iodine (I) recombination, 4.3 x 10 to the 11th power (1.9) + or - cu cm/s; for n-C3F7I stabilized atomic iodine recombination (I + I) 3.7 x 10 to the -32nd power (2.3) + or -1 cm to the 6th power/s; and for molecular iodine (I2) quenching, 3.1 x 10 to the -11th power (1.6) + or - 1 cu cm/s. These rates are consistent with the recent measurements.

  10. Kinetic Simulations of Rayleigh-Taylor Instabilities

    CERN Document Server

    Sagert, Irina; Colbry, Dirk; Howell, Jim; Staber, Alec; Strother, Terrance

    2014-01-01

    We report on an ongoing project to develop a large scale Direct Simulation Monte Carlo code. The code is primarily aimed towards applications in astrophysics such as simulations of core-collapse supernovae. It has been tested on shock wave phenomena in the continuum limit and for matter out of equilibrium. In the current work we focus on the study of fluid instabilities. Like shock waves these are routinely used as test-cases for hydrodynamic codes and are discussed to play an important role in the explosion mechanism of core-collapse supernovae. As a first test we study the evolution of a single-mode Rayleigh-Taylor instability at the interface of a light and a heavy fluid in the presence of a gravitational acceleration. To suppress small-wavelength instabilities caused by the irregularity in the separation layer we use a large particle mean free path. The latter leads to the development of a diffusion layer as particles propagate from one fluid into the other. For small amplitudes, when the instability is i...

  11. Kinetic Simulations of Particle Acceleration at Shocks

    Energy Technology Data Exchange (ETDEWEB)

    Caprioli, Damiano [Princeton University; Guo, Fan [Los Alamos National Laboratory

    2015-07-16

    Collisionless shocks are mediated by collective electromagnetic interactions and are sources of non-thermal particles and emission. The full particle-in-cell approach and a hybrid approach are sketched, simulations of collisionless shocks are shown using a multicolor presentation. Results for SN 1006, a case involving ion acceleration and B field amplification where the shock is parallel, are shown. Electron acceleration takes place in planetary bow shocks and galaxy clusters. It is concluded that acceleration at shocks can be efficient: >15%; CRs amplify B field via streaming instability; ion DSA is efficient at parallel, strong shocks; ions are injected via reflection and shock drift acceleration; and electron DSA is efficient at oblique shocks.

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

    International Nuclear Information System (INIS)

    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

  13. Kinetic simulations of plasmoid chain dynamics

    International Nuclear Information System (INIS)

    The dynamics of a plasmoid chain is studied with three dimensional Particle-in-Cell simulations. The evolution of the system with and without a uniform guide field, whose strength is 1/3 the asymptotic magnetic field, is investigated. The plasmoid chain forms by spontaneous magnetic reconnection: the tearing instability rapidly disrupts the initial current sheet generating several small-scale plasmoids that rapidly grow in size coalescing and kinking. The plasmoid kink is mainly driven by the coalescence process. It is found that the presence of guide field strongly influences the evolution of the plasmoid chain. Without a guide field, a main reconnection site dominates and smaller reconnection regions are included in larger ones, leading to an hierarchical structure of the plasmoid-dominated current sheet. On the contrary in presence of a guide field, plasmoids have approximately the same size and the hierarchical structure does not emerge, a strong core magnetic field develops in the center of the plasmoid in the direction of the existing guide field, and bump-on-tail instability, leading to the formation of electron holes, is detected in proximity of the plasmoids

  14. Exact non-additive kinetic potentials in realistic chemical systems.

    Science.gov (United States)

    de Silva, Piotr; Wesolowski, Tomasz A

    2012-09-01

    In methods based on frozen-density embedding theory or subsystem formulation of density functional theory, the non-additive kinetic potential (v(t)(nad)(r)) needs to be approximated. Since v(t)(nad)(r) is defined as a bifunctional, the common strategies rely on approximating v(t)(nad)[ρ(A),ρ(B)](r). In this work, the exact potentials (not bifunctionals) are constructed for chemically relevant pairs of electron densities (ρ(A) and ρ(B)) representing: dissociating molecules, two parts of a molecule linked by a covalent bond, or valence and core electrons. The method used is applicable only for particular case, where ρ(A) is a one-electron or spin-compensated two-electron density, for which the analytic relation between the density and potential exists. The sum ρ(A) + ρ(B) is, however, not limited to such restrictions. Kohn-Sham molecular densities are used for this purpose. The constructed potentials are analyzed to identify the properties which must be taken into account when constructing approximations to the corresponding bifunctional. It is comprehensively shown that the full von Weizsäcker component is indispensable in order to approximate adequately the non-additive kinetic potential for such pairs of densities. PMID:22957558

  15. Variable elimination in chemical reaction networks with mass action kinetics

    CERN Document Server

    Feliu, Elisenda

    2011-01-01

    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 of variables. The procedure reduces the variables in the system to a set of "core" variables by eliminating variables corresponding to a set of non-interacting species. The steady states are parameterized algebraically by the core variables, and a graphical condition is given for when a steady state with positive core variables necessarily have all variables positive. Further, we characterize graphically the sets of eliminated variables that are constrained by a conservation law and show that this conservation law takes a specific form.

  16. 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.

  17. Kinetic Energy-Based Temperature Computation in Non-Equilibrium Molecular Dynamics Simulation

    OpenAIRE

    Liu, Bin; Xu, Ran; He, Xiaoqiao

    2009-01-01

    The average kinetic energy is widely used to characterize temperature in molecular dynamics (MD) simulation. In this letter, the applicability of three types of average kinetic energy as measures of temperature is investigated, i.e., the total kinetic energy, kinetic energy without the centroid translation part, and thermal disturbance kinetic energy. Our MD simulations indicate that definitions of temperature based on the kinetic energy including rigid translational or rotational motion may ...

  18. Partially-Collisional Plasma Simulation using Complex Particle Kinetics

    Science.gov (United States)

    Larson, David; Hewett, Dennis

    2003-10-01

    Unlike traditional PIC particles, the CPK (Complex Particle Kinetics) algorithm [1] allows particles with a Gaussian spatial profile and a Mawellian velocity distribution to evolve self-consistently. These particles are then split spatially and/or in velocity to probe for emerging features as the simulation progresses. Aggressive merging is employed to control the number of simulation particles. The combination of the CPK algorithm with our new collision algorithm [2] should allow simulation of plasmas in the previously cost-prohibitive partially-collisional regime. Results from one-dimensional simulations will be compared to experimental data and 2 and 3-D results will be discussed in the context of energetic high altitude events. [1] D.W. Hewett, 'Fragmentation, merging, and internal dynamics for PIC simulation with finite size particles,' accepted by J. Comp. Phys. (2003). [2] D. J. Larson, 'A Coulomb Collision Model for PIC Plasma Simulation,' J. Comp. Phys. 188 (2003).

  19. 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 and......-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....

  20. Efficient procedures for the numerical simulation of mid-size RNA kinetics

    Directory of Open Access Journals (Sweden)

    Aviram Iddo

    2012-09-01

    Full Text Available Abstract Motivation Methods for simulating the kinetic folding of RNAs by numerically solving the chemical master equation have been developed since the late 90's, notably the programs Kinfold and Treekin with Barriers that are available in the Vienna RNA package. Our goal is to formulate extensions to the algorithms used, starting from the Gillespie algorithm, that will allow numerical simulations of mid-size (~ 60–150 nt RNA kinetics in some practical cases where numerous distributions of folding times are desired. These extensions can contribute to analyses and predictions of RNA folding in biologically significant problems. Results By describing in a particular way the reduction of numerical simulations of RNA folding kinetics into the Gillespie stochastic simulation algorithm for chemical reactions, it is possible to formulate extensions to the basic algorithm that will exploit memoization and parallelism for efficient computations. These can be used to advance forward from the small examples demonstrated to larger examples of biological interest. Software The implementation that is described and used for the Gillespie algorithm is freely available by contacting the authors, noting that the efficient procedures suggested may also be applicable along with Vienna's Kinfold.

  1. Simulation of the kinetics of precipitation reactions in ferritic steels

    International Nuclear Information System (INIS)

    Computer simulations of diffusion-controlled phase transformations in model alloys of Fe-Cr-C, Fe-Cr-W-C, Fe-Cr-Si-C, and Fe-Cr-Co-V-C are presented. The compositions considered are typical for ferritic steels. The simulations are performed using the software DICTRA and the thermodynamic calculations of phase equilibria are performed using Thermo-Calc. The thermodynamic driving forces and the kinetics of diffusion-controlled precipitation reactions of M23C6, M7C3, cementite and Laves-phase (Fe, Cr)2W are discussed. The simultaneous growth of stable and metastable phases is treated in a multi-cell approach. The results show remarkable effects on the growth kinetics due to the competition during simultaneous growth

  2. 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.

  3. HCT, Time Dependent 1-D Gas Hydrodynamics, Chemical Kinetics, Chemical Transport

    International Nuclear Information System (INIS)

    1 - Description of program or function: HCT is a general program for calculating time-dependent problems involving one-dimensional gas hydrodynamics, transport, and detailed chemical kinetics. It is capable of modeling in detail one-dimensional time-dependent combustion phenomena of gases. The physical processes modeled are chemical reactions, thermal conduction, species diffusion, and hydrodynamics. Problem initialization is by input deck; output available includes a complete set of general line printer edits. The basic difference equations allow one to efficiently calculate stiff kinetics systems and systems evolving slowly compared to sound transit times. Hydrodynamics calculation may be done in either a Lagrange or Eulerian framework. An option gives a variable spatial mesh with high resolution in areas of high-temperature gradients. 2 - Method of solution: For maximum robustness, the implicitly differenced hydrodynamics, transport, and kinetics equations are solved simultaneously using a generalized Newton iteration scheme. This method requires the inversion of a block tridiagonal matrix with block size proportional to the number of species. Optimized assembly language matrix-manipulation routines which take advantage of the CDC7600 pipeline architecture are included

  4. Kinetic simulation study of one dimensional collisional bounded plasma

    Institute of Scientific and Technical Information of China (English)

    1999-01-01

    A self-consistent kinetic simulation study ofone dimensional collisional bounded plasma is presented.The formation of stable sheath potential is investigated.It is found that mass ratio of electron and ion not onlyaffects the level of sheath potential, but also affectsthe ion temperature of system. It is clarified that the effects of secondaryemission electron on both the total potential dropand the temperature are not important.

  5. Non-linear punctual kinetics applied to PWR reactors simulation

    International Nuclear Information System (INIS)

    In order to study some kinds of nuclear reactor accidents, a simulation is made using the punctual kinetics model for the reactor core. The following integration methods are used: Hansen's method in which a linearization is made and CSMP using a variable interval fourth-order Runge Kutta method. The results were good and were compared with those obtained by the code Dinamica I which uses a finite difference integration method of backward kind. (Author)

  6. Vlasov simulations of kinetic Alfvén waves at proton kinetic scales

    Energy Technology Data Exchange (ETDEWEB)

    Vásconez, C. L. [Dipartimento di Fisica, Università della Calabria, I-87036 Cosenza (Italy); Observatorio Astronómico de Quito, Escuela Politécnica Nacional, Quito (Ecuador); Valentini, F.; Veltri, P. [Dipartimento di Fisica, Università della Calabria, I-87036 Cosenza (Italy); Camporeale, E. [Centrum Wiskunde and Informatica, Amsterdam (Netherlands)

    2014-11-15

    Kinetic Alfvén waves represent an important subject in space plasma physics, since they are thought to play a crucial role in the development of the turbulent energy cascade in the solar wind plasma at short wavelengths (of the order of the proton gyro radius ρ{sub p} and/or inertial length d{sub p} and beyond). A full understanding of the physical mechanisms which govern the kinetic plasma dynamics at these scales can provide important clues on the problem of the turbulent dissipation and heating in collisionless systems. In this paper, hybrid Vlasov-Maxwell simulations are employed to analyze in detail the features of the kinetic Alfvén waves at proton kinetic scales, in typical conditions of the solar wind environment (proton plasma beta β{sub p} = 1). In particular, linear and nonlinear regimes of propagation of these fluctuations have been investigated in a single-wave situation, focusing on the physical processes of collisionless Landau damping and wave-particle resonant interaction. Interestingly, since for wavelengths close to d{sub p} and β{sub p} ≃ 1 (for which ρ{sub p} ≃ d{sub p}) the kinetic Alfvén waves have small phase speed compared to the proton thermal velocity, wave-particle interaction processes produce significant deformations in the core of the particle velocity distribution, appearing as phase space vortices and resulting in flat-top velocity profiles. Moreover, as the Eulerian hybrid Vlasov-Maxwell algorithm allows for a clean almost noise-free description of the velocity space, three-dimensional plots of the proton velocity distribution help to emphasize how the plasma departs from the Maxwellian configuration of thermodynamic equilibrium due to nonlinear kinetic effects.

  7. Communication: Consistent interpretation of molecular simulation kinetics using Markov state models biased with external information

    Science.gov (United States)

    Rudzinski, Joseph F.; Kremer, Kurt; Bereau, Tristan

    2016-02-01

    Molecular simulations can provide microscopic insight into the physical and chemical driving forces of complex molecular processes. Despite continued advancement of simulation methodology, model errors may lead to inconsistencies between simulated and reference (e.g., from experiments or higher-level simulations) observables. To bound the microscopic information generated by computer simulations within reference measurements, we propose a method that reweights the microscopic transitions of the system to improve consistency with a set of coarse kinetic observables. The method employs the well-developed Markov state modeling framework to efficiently link microscopic dynamics with long-time scale constraints, thereby consistently addressing a wide range of time scales. To emphasize the robustness of the method, we consider two distinct coarse-grained models with significant kinetic inconsistencies. When applied to the simulated conformational dynamics of small peptides, the reweighting procedure systematically improves the time scale separation of the slowest processes. Additionally, constraining the forward and backward rates between metastable states leads to slight improvement of their relative stabilities and, thus, refined equilibrium properties of the resulting model. Finally, we find that difficulties in simultaneously describing both the simulated data and the provided constraints can help identify specific limitations of the underlying simulation approach.

  8. 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:…

  9. 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.

  10. Atomistic Kinetic Monte Carlo Simulations of Polycrystalline Copper Electrodeposition

    CERN Document Server

    Treeratanaphitak, Tanyakarn; Abukhdeir, Nasser Mohieddin

    2014-01-01

    A high-fidelity kinetic Monte Carlo (KMC) simulation method (T. Treeratanaphitak, M. Pritzker, N. M. Abukhdeir, Electrochim. Acta 121 (2014) 407--414) using the semi-empirical multi-body embedded-atom method (EAM) potential has been extended to model polycrystalline metal electrodeposition. The presented KMC-EAM method enables true three-dimensional atomistic simulations of electrodeposition over experimentally relevant timescales. Simulations using KMC-EAM are performed over a range of overpotentials to predict the effect on deposit texture evolution. Results show strong agreement with past experimental results both with respect to deposition rates on various copper surfaces and roughness-time power law behaviour. It is found that roughness scales with time $\\propto t^\\beta$ where $\\beta=0.62 \\pm 0.12$, which is in good agreement with past experimental results. Furthermore, the simulations provide insights into sub-surface deposit morphologies which are not directly accessible from experimental measurements.

  11. Melting behavior of typical thermoplastic materials – An experimental and chemical kinetics study

    International Nuclear Information System (INIS)

    Highlights: • A new medium-scale melting and pyrolysis experiment instrument for thermoplastics was designed. • The thermal hazard induced by melting and dripping of thermoplastics was studied. • The medium-scale experimental results on the thermoplastics pyrolysis suggest some limit for TGA tests. -- Abstract: A medium-scale melting experiment rig was designed and constructed in this study. A detailed experimental study was conducted on the melting behavior and the chemical kinetic characteristics of three typical thermoplastic materials, including polypropylene (PP), polyethylene (PE) and polystyrene (PS). It is observed that the thermal decomposition of the thermoplastic materials mainly consists of three stages: the initial heating stage, the melting-dominated stage and the gasification-dominated stage. Melting of the materials examined takes place within a certain temperature range. The melting temperature of PS is the lowest, moreover, it takes the shortest time to be completely liquefied. To quantitatively represent the chemical kinetics, an nth-order reaction model was employed to interpret the thermal decomposition behavior of the materials. The calculated reaction order is largely in accordance with the small-scale thermal gravimetric analysis (TGA). The small difference between the results and TGA data suggests that there are some limitations in the small-scale experiments in simulating the behavior of thermoplastic materials in a thermal hazard. Therefore, investigating the thermal physical and chemical properties of the thermoplastic materials and their thermal hazard prevention in medium or large-scale experiments is necessary for the fire safety considerations of polymer materials

  12. Multi-level Monte Carlo for stochastically modeled chemical kinetic systems

    CERN Document Server

    Anderson, David F

    2011-01-01

    A chemical reaction network involves multiple reactions and species. The simplest stochastic models of such networks treat the system as a continuous time Markov chain with the state being the number of molecules of each species and with reactions modeled as possible transitions of the chain. While there are methods that generate exact sample paths of the Markov chain, their computational cost scales linearly with the number of reaction events. Therefore, such methods become computationally intense for even moderately sized systems. This drawback is greatly exacerbated when such simulations are performed in conjunction with Monte Carlo techniques, as is the norm, which require the generation of many paths. We show how to extend a recently proposed multi-level Monte Carlo approach to this stochastic chemical kinetic setting, lowering the computational complexity needed to compute expected values of functions of the state of the system to a specified accuracy. The extension is non-trivial and a novel coupling o...

  13. 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.

  14. 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.

  15. Plasma sheath studies using the kinetic trajectory simulation model

    International Nuclear Information System (INIS)

    Plasma sheath formed in front of a material wall for different cases have been studied. For given electron and ion distributions at the sheath entrance we use Kinetic Trajectory Simulation (KTS) model to obtain the solution to a non-neutral, time-independent, collisionless plasma sheath. The characteristic feature of the KTS method is that the distribution functions of the particle species involved are calculated directly by solving the related kinetic equations along the respective collisionless particle trajectories. For a given potential distribution, we calculate the exact ion distribution function by integrating Vlasov's equation along its characteristics and taking into account the scraping-off effect at the wall. The electron distribution, on the other hand, is calculated analytically, however taking into account the cut-off introduced by electron absorption at the wall.We also present a scheme for coupling a quasineutral two-fluid (electron-ion) presheath solution to a non-neutral, collisionless kinetic sheath solution for a 1d1v case. It has been observed that the sheath structure is highly influenced by the magnitude of potential applied to the wall. The applied kinetic model is thus expected to give better insight to the sheath phenomena. (author)

  16. 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.

  17. Methods of nonlinear kinetics

    OpenAIRE

    Gorban, A. N.; Karlin, I. V.

    2003-01-01

    Nonlinear kinetic equations are reviewed for a wide audience of specialists and postgraduate students in physics, mathematical physics, material science, chemical engineering and interdisciplinary research. Contents: The Boltzmann equation, Phenomenology and Quasi-chemical representation of the Boltzmann equation, Kinetic models, Discrete velocity models, Direct simulation, Lattice Gas and Lattice Boltzmann models, Minimal Boltzmann models for flows at low Knudsen number, Other kinetic equati...

  18. GPU enabled kinetic effects in radio-frequency heating simulation

    Science.gov (United States)

    Green, David; RF-SciDAC Collaboration

    2015-11-01

    In previous work we have demonstrated the iterative addition of parallel kinetic effects to finite-difference frequency-domain simulation of radio-frequency (RF) wave propagation in fusion relevant plasmas. Such iterative addition in configuration space bypasses several of the difficulties with traditional spectral methods for kinetic RF simulation when applied to problems that exhibit non-periodic geometries. Furthermore, the direct numerical integration of particle trajectories in real magnetic field geometries removes violations of the stationary phase approximation inherent in the spectral approach. Here we extend this method to include perpendicular kinetics by relying on the massively parallel capability of GPUs to enable resolution of 3 velocity-space dimensions. We present results for a mode converted ion Bernstein wave scenario in 1-space plus 3-velocity dimensions case relevant to fusion plasmas. This research used resources of the OLCF at ORNL, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725.

  19. Modeling and Computer Simulation: Molecular Dynamics and Kinetic Monte Carlo

    Energy Technology Data Exchange (ETDEWEB)

    Wirth, B.D.; Caturla, M.J.; Diaz de la Rubia, T.

    2000-10-10

    Recent years have witnessed tremendous advances in the realistic multiscale simulation of complex physical phenomena, such as irradiation and aging effects of materials, made possible by the enormous progress achieved in computational physics for calculating reliable, yet tractable interatomic potentials and the vast improvements in computational power and parallel computing. As a result, computational materials science is emerging as an important complement to theory and experiment to provide fundamental materials science insight. This article describes the atomistic modeling techniques of molecular dynamics (MD) and kinetic Monte Carlo (KMC), and an example of their application to radiation damage production and accumulation in metals. It is important to note at the outset that the primary objective of atomistic computer simulation should be obtaining physical insight into atomic-level processes. Classical molecular dynamics is a powerful method for obtaining insight about the dynamics of physical processes that occur on relatively short time scales. Current computational capability allows treatment of atomic systems containing as many as 10{sup 9} atoms for times on the order of 100 ns (10{sup -7}s). The main limitation of classical MD simulation is the relatively short times accessible. Kinetic Monte Carlo provides the ability to reach macroscopic times by modeling diffusional processes and time-scales rather than individual atomic vibrations. Coupling MD and KMC has developed into a powerful, multiscale tool for the simulation of radiation damage in metals.

  20. 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

  1. 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

  2. Kinetic Simulation and Energetic Neutral Atom Imaging of the Magnetosphere

    Science.gov (United States)

    Fok, Mei-Ching H.

    2011-01-01

    Advanced simulation tools and measurement techniques have been developed to study the dynamic magnetosphere and its response to drivers in the solar wind. The Comprehensive Ring Current Model (CRCM) is a kinetic code that solves the 3D distribution in space, energy and pitch-angle information of energetic ions and electrons. Energetic Neutral Atom (ENA) imagers have been carried in past and current satellite missions. Global morphology of energetic ions were revealed by the observed ENA images. We have combined simulation and ENA analysis techniques to study the development of ring current ions during magnetic storms and substorms. We identify the timing and location of particle injection and loss. We examine the evolution of ion energy and pitch-angle distribution during different phases of a storm. In this talk we will discuss the findings from our ring current studies and how our simulation and ENA analysis tools can be applied to the upcoming TRIO-CINAMA mission.

  3. Kinetic modeling and exploratory numerical simulation of chloroplastic starch degradation

    Directory of Open Access Journals (Sweden)

    Nag Ambarish

    2011-06-01

    Full Text Available Abstract Background Higher plants and algae are able to fix atmospheric carbon dioxide through photosynthesis and store this fixed carbon in large quantities as starch, which can be hydrolyzed into sugars serving as feedstock for fermentation to biofuels and precursors. Rational engineering of carbon flow in plant cells requires a greater understanding of how starch breakdown fluxes respond to variations in enzyme concentrations, kinetic parameters, and metabolite concentrations. We have therefore developed and simulated a detailed kinetic ordinary differential equation model of the degradation pathways for starch synthesized in plants and green algae, which to our knowledge is the most complete such model reported to date. Results Simulation with 9 internal metabolites and 8 external metabolites, the concentrations of the latter fixed at reasonable biochemical values, leads to a single reference solution showing β-amylase activity to be the rate-limiting step in carbon flow from starch degradation. Additionally, the response coefficients for stromal glucose to the glucose transporter kcat and KM are substantial, whereas those for cytosolic glucose are not, consistent with a kinetic bottleneck due to transport. Response coefficient norms show stromal maltopentaose and cytosolic glucosylated arabinogalactan to be the most and least globally sensitive metabolites, respectively, and β-amylase kcat and KM for starch to be the kinetic parameters with the largest aggregate effect on metabolite concentrations as a whole. The latter kinetic parameters, together with those for glucose transport, have the greatest effect on stromal glucose, which is a precursor for biofuel synthetic pathways. Exploration of the steady-state solution space with respect to concentrations of 6 external metabolites and 8 dynamic metabolite concentrations show that stromal metabolism is strongly coupled to starch levels, and that transport between compartments serves to

  4. 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...

  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. 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

  7. Magnetic null points in kinetic simulations of space plasmas

    CERN Document Server

    Olshevsky, Vyacheslav; Divin, Andrey; Peng, Ivy Bo; Markidis, Stefano; Innocenti, Maria Elena; Cazzola, Emanuele; Lapenta, Giovanni

    2015-01-01

    We present a systematic attempt to study magnetic null points and the associated magnetic energy conversion in kinetic Particle-in-Cell simulations of various plasma configurations. We address three-dimensional simulations performed with the semi-implicit kinetic electromagnetic code iPic3D in different setups: variations of a Harris current sheet, dipolar and quadrupolar magnetospheres interacting with the solar wind; and a relaxing turbulent configuration with multiple null points. Spiral nulls are more likely created in space plasmas: in all our simulations except lunar magnetic anomaly and quadrupolar mini-magnetosphere the number of spiral nulls prevails over the number of radial nulls by a factor of 3-9. We show that often magnetic nulls do not indicate the regions of intensive energy dissipation. Energy dissipation events caused by topological bifurcations at radial nulls are rather rare and short-lived. The so-called X-lines formed by the radial nulls in the Harris current sheet and lunar magnetic ano...

  8. Chemical mixing in smoothed particle hydrodynamics simulations

    CERN Document Server

    Greif, Thomas H; Bromm, Volker; Klessen, Ralf S

    2008-01-01

    We introduce a simple and efficient algorithm for diffusion in smoothed particle hydrodynamics (SPH) simulations and apply it to the problem of chemical mixing. Based on the concept of turbulent diffusion, we link the diffusivity of a pollutant to the local physical conditions and can thus resolve mixing in space and time. We apply our prescription to the evolution of an idealized supernova remnant and find that we can model the distribution of heavy elements without having to explicitly resolve hydrodynamic instabilities in the post-shock gas. Instead, the dispersal of the pollutant is implicitly modeled through its dependence on the local velocity dispersion. Our method can thus be used in any SPH simulation that investigates chemical mixing but lacks the necessary resolution on small scales. Potential applications include the enrichment of the interstellar medium in present-day galaxies, as well as the intergalactic medium at high redshifts.

  9. Chemical mixing in smoothed particle hydrodynamics simulations

    Science.gov (United States)

    Greif, Thomas H.; Glover, Simon C. O.; Bromm, Volker; Klessen, Ralf S.

    2009-02-01

    We introduce a simple and efficient algorithm for diffusion in smoothed particle hydrodynamics (SPH) simulations and apply it to the problem of chemical mixing. Based on the concept of turbulent diffusion, we link the diffusivity of a pollutant to the local physical conditions and can thus resolve mixing in space and time. We apply our prescription to the evolution of an idealized supernova remnant and find that we can model the distribution of heavy elements without having to explicitly resolve hydrodynamic instabilities in the post-shock gas. Instead, the dispersal of the pollutant is implicitly modelled through its dependence on the local velocity dispersion. Our method can thus be used in any SPH simulation that investigates chemical mixing but lacks the necessary resolution on small scales. Potential applications include the enrichment of the interstellar medium in present-day galaxies, as well as the intergalactic medium at high redshifts.

  10. Thermodynamic and kinetic simulation of transient liquid-phase bonding

    Science.gov (United States)

    Lindner, Brad

    The use of numeric computational methods for the simulation of materials systems is becoming more prevalent and an understanding of these tools may soon be a necessity for Materials Engineers and Scientists. The applicability of numerical simulation methods to transient liquid-phase (TLP) bonding is evaluated using a type 316L/MBF-51 material system. The comparisons involve the calculation of bulk diffusivities, tracking of interface positions during dissolution, widening, and isothermal solidification stages, as well as comparison of elemental composition profiles. The simulations were performed with Thermo-Calc and DICTRA software packages and the experiments with differential scanning calorimetry (DSC), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and optical microscopic methods. Analytical methods are also discussed to enhance understanding. The results of the investigation show that while general agreement between simulations and experiments can be obtained, assumptions made with the simulation programs may cause difficulty in interpretation of the results unless the user has sufficient, mathematical, thermodynamic, kinetic, and simulation background.

  11. Intermediate-high energy nuclear reaction kinetics simulation and QMD

    International Nuclear Information System (INIS)

    The main features of the IHENRKS and its application in the study of thermalization for reaction of 830 MeV P + 56Fe are described. IHENRKS is the abbreviation of intermediate-high energy nuclear reaction kinetic simulation. It combines the idea and method of MCM, SSIENC and QMD. These kind of models treat the movement of each particle (nucleon and meson) and their collisions in time and space and concern with the new particle production. From calculations for 830 MeV proton bombarding reactions, it can be concluded that the nucleus is not wholly thermalized, but locally thermalized. (1 fig.)

  12. 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.

  13. Theory of chemical kinetics and charge transfer based on nonequilibrium thermodynamics.

    Science.gov (United States)

    Bazant, Martin Z

    2013-05-21

    the past 7 years, which is capable of answering these questions. The reaction rate is a nonlinear function of the thermodynamic driving force, the free energy of reaction, expressed in terms of variational chemical potentials. The theory unifies and extends the Cahn-Hilliard and Allen-Cahn equations through a master equation for nonequilibrium chemical thermodynamics. For electrochemistry, I have also generalized both Marcus and Butler-Volmer kinetics for concentrated solutions and ionic solids. This new theory provides a quantitative description of LFP phase behavior. Concentration gradients and elastic coherency strain enhance the intercalation rate. At low currents, the charge-transfer rate is focused on exposed phase boundaries, which propagate as "intercalation waves", nucleated by surface wetting. Unexpectedly, homogeneous reactions are favored above a critical current and below a critical size, which helps to explain the rate capability of LFP nanoparticles. Contrary to other mechanisms, elevated temperatures and currents may enhance battery performance and lifetime by suppressing phase separation. The theory has also been extended to porous electrodes and could be used for battery engineering with multiphase active materials. More broadly, the theory describes nonequilibrium chemical systems at mesoscopic length and time scales, beyond the reach of molecular simulations and bulk continuum models. The reaction rate is consistently defined for inhomogeneous, nonequilibrium states, for example, with phase separation, large electric fields, or mechanical stresses. This research is also potentially applicable to fluid extraction from nanoporous solids, pattern formation in electrophoretic deposition, and electrochemical dynamics in biological cells. PMID:23520980

  14. Modeling and computational simulation of adsorption based chemical heat pumps

    International Nuclear Information System (INIS)

    In this study a methodology is developed for the design of a packed bed reactor to be used in a Chemical Heat Pump (CHP). Adsorption and desorption of ethanol on active carbon packing in the reactor are investigated. Depending on the cycle, i.e. adsorption or desorption, cooling or heating of the reactor material is modeled through transient energy equation. The parameters associated with the vapor-carbon adsorption kinetics are experimentally determined. Then spatial distribution of temperature and adsorbed vapor amount are obtained with respect to time in adsorption–desorption cycles. These profiles are used to predict heating or cooling powers and COP for different adsorbent bed geometries and adsorption/desorption cycle times. Strong effect of heat transfer resistance of the packing, hence reactor size, on the system performance is observed. - Highlights: ► Performance of a chemical pump reactor is investigated theoretically. ► Ethanol adsorption/desorption on active carbon packing is modeled and simulated. ► Adsorption/desorption kinetics and equilibrium relations are found experimentally.

  15. Numerical kinetic model including equilibrium and rate equations for chemical reactions of actinide elements

    International Nuclear Information System (INIS)

    Numerical simulation method was examined for chemical reactions of actinide elements U, Pu, Np, and Tc etc. in an aqueous nitric acid solution. It is known that the numerical calculation for the Purex process with chemical reactions and liquid flow becomes stiff, because time constant for the chemical reactions is two to three order of magnitude smaller due to the very fast reactions than that of mass transfer or of reaching distribution equilibrium. Recently in order to increase a time step Δt the partial equilibrium (P.E.) model, in which some very fast reactions are treated by the equilibrium law whereas other reactions are by the rate law, has been proposed. In the present study concentration change of the solutes in an aqueous solution with 30 chemical reactions, of which 4 are expressed by equilibrium equations, has been calculated. Description of the P.E. model and the comparison of the results and cpu time between the kinetic and the P.E. models are given. (author)

  16. Kinetic simulations of secondary reconnection in the reconnection jet

    Science.gov (United States)

    Huang, S. Y.; Zhou, M.; Yuan, Z. G.; Fu, H. S.; He, J. S.; Sahraoui, F.; Aunai, N.; Deng, X. H.; Fu, S.; Pang, Y.; Wang, D. D.

    2015-08-01

    Magnetic reconnection, as one important energy dissipation process in plasmas, has been extensively studied in the past several decades. Magnetic reconnection occurring in the downstream of a primary X line is referred to as secondary reconnection. In this paper, we used kinetic simulations to investigate the secondary reconnection in detail. We found that secondary reconnection is reversed by the compression caused by the outflowing jet originating from the primary reconnection site, which results in the erosion of the magnetic island between the two X lines within ~3 ωci-1. We show the observational signatures expected in electromagnetic fields and plasma measurements in the Earth's magnetotail, associated with this mechanism. These simulation results could be applied to interpret the signatures associated with the evolution of earthward magnetic islands in the Earth's magnetotail.

  17. Kinetics of a Multilamellar Lipid Vesicle Ripening: Simulation and Theory.

    Science.gov (United States)

    Xu, Rui; He, Xuehao

    2016-03-10

    Lipid vesicle ripening via unimolecular diffusion and exchange greatly influences the evolution of complex vesicle structure. However, this behavior is difficult to capture using conventional experimental technology and molecular simulation. In the present work, the ripening of a multilamellar lipid vesicle (MLV) is effectively explored using a mesoscale coarse-grained molecular model. The simulation reveals that a small MLV evolves into a unilamellar vesicle over a very long time period. In this process, only the outermost bilayer inflates, and the inner bilayers shrink. With increasing MLV size, the ripening process becomes complex and depends on competition between a series of adjacent bilayers in the MLV. To understand the diffusion behavior of the unimolecule, the potentials of mean force (PMFs) of a single lipid molecule across unilamellar vesicles with different sizes are calculated. It is found that the PMF of lipid dissociation from the inner layer is different than that of the outer layer, and the dissociation energy barrier sensitively depends on the curvature of the bilayer. A kinetics theoretical model of MLV ripening that considers the lipid dissociation energy for curved bilayers is proposed. The model successfully interprets the MLV ripening process with various numbers of bilayers and shows potential to predict the ripening kinetics of complex lipid vesicles. PMID:26882997

  18. 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...

  19. Large-scale reactive molecular dynamics simulation and kinetic modeling of high-temperature pyrolysis of the Gloeocapsomorphaprisca microfossils.

    Science.gov (United States)

    Zou, Chenyu; Raman, Sumathy; van Duin, Adri C T

    2014-06-12

    The ability to predict accurately the thermal conversion of complex carbonaceous materials is of value in both petroleum exploration and refining operations. Modeling the thermal cracking of kerogen under basinal heating conditions improves the predrill prediction of oil and gas yields and quality, thereby ultimately lowering the exploration risk. Modeling the chemical structure and reactivity of asphaltene from petroleum vacuum residues enables prediction of coke formation and properties in refinery processes, thereby lowering operating cost. The chemical structure-chemical yield modeling (CS-CYM) developed by Freund et al. is more rigorous, time-consuming, and requires a great deal of chemical insight into reaction network and reaction kinetics. The present work explores the applicability of a more fundamental atomistic simulation using the quantum mechanically based reactive force field to predict the product yield and overall kinetics of decomposition of two biopolymers, namely, the Kukersite and Gutternberg. Reactive molecular dynamics (RMD) simulations were performed on systems consisting of 10(4) to 10(5) atoms at different densities and temperatures to derive the overall kinetic parameters and a lumped kinetic model for pyrolysis. The kinetic parameters derived from the simulated pyrolysis of an individual component and the mixture of all four components in Guttenberg reveal the role of cross-talk between the fragments and enhanced reactivity of component A by radicals from other components. The Arrhenius extrapolation of the model yields reasonable prediction for the overall barrier for cracking. Because simulations were run at very high temperature (T > 1500 K) to study cracking within the simulation time of up to 1 ns, it, however, led to the entropically favored ethylene formation as a dominant decomposition route. Future work will focus on evaluating the applicability of accelerated reactive MD approaches to study cracking. PMID:24821589

  20. A Monte Carlo simulation for kinetic chemotaxis models: an application to the traveling population wave

    CERN Document Server

    Yasuda, Shugo

    2015-01-01

    A Monte Carlo simulation for the chemotactic bacteria is developed on the basis of the kinetic modeling, i.e., the Boltzmann transport equation, and applied to the one-dimensional traveling population wave in a micro channel.In this method, the Monte Carlo method, which calculates the run-and-tumble motions of bacteria, is coupled with a finite volume method to solve the macroscopic transport of the chemical cues in the field. The simulation method can successfully reproduce the traveling population wave of bacteria which was observed experimentally. The microscopic dynamics of bacteria, e.g., the velocity autocorrelation function and velocity distribution function of bacteria, are also investigated. It is found that the bacteria which form the traveling population wave create quasi-periodic motions as well as a migratory movement along with the traveling population wave. Simulations are also performed with changing the sensitivity and modulation parameters in the response function of bacteria. It is found th...

  1. Aerosol simulation including chemical and nuclear reactions

    Energy Technology Data Exchange (ETDEWEB)

    Marwil, E.S.; Lemmon, E.C.

    1985-01-01

    The numerical simulation of aerosol transport, including the effects of chemical and nuclear reactions presents a challenging dynamic accounting problem. Particles of different sizes agglomerate and settle out due to various mechanisms, such as diffusion, diffusiophoresis, thermophoresis, gravitational settling, turbulent acceleration, and centrifugal acceleration. Particles also change size, due to the condensation and evaporation of materials on the particle. Heterogeneous chemical reactions occur at the interface between a particle and the suspending medium, or a surface and the gas in the aerosol. Homogeneous chemical reactions occur within the aersol suspending medium, within a particle, and on a surface. These reactions may include a phase change. Nuclear reactions occur in all locations. These spontaneous transmutations from one element form to another occur at greatly varying rates and may result in phase or chemical changes which complicate the accounting process. This paper presents an approach for inclusion of these effects on the transport of aerosols. The accounting system is very complex and results in a large set of stiff ordinary differential equations (ODEs). The techniques for numerical solution of these ODEs require special attention to achieve their solution in an efficient and affordable manner. 4 refs.

  2. 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.

  3. Kiche; A Simulation tool for kinetics of iodine chemistry in the containment of light water reactors under severe accident conditions (Contract research)

    OpenAIRE

    森山 清史; 丸山 結; 中村 秀夫

    2011-01-01

    An iodine chemistry simulation tool, Kiche, was developed for analyses of chemical kinetics relevant to iodine volatilization in the containment vessel of light water reactors (LWRs) during a severe accident. It consists of a Fortran code to solve chemical kinetics models, reaction databases written in plain text format, and peripheral tools to convert the reaction databases into Fortran codes. Potential advantages of Kiche are the text format reaction database separated from the code that pr...

  4. Monte Carlo simulation on kinetics of batch and semi-batch free radical polymerization

    KAUST Repository

    Shao, Jing

    2015-10-27

    Based on Monte Carlo simulation technology, we proposed a hybrid routine which combines reaction mechanism together with coarse-grained molecular simulation to study the kinetics of free radical polymerization. By comparing with previous experimental and simulation studies, we showed the capability of our Monte Carlo scheme on representing polymerization kinetics in batch and semi-batch processes. Various kinetics information, such as instant monomer conversion, molecular weight, and polydispersity etc. are readily calculated from Monte Carlo simulation. The kinetic constants such as polymerization rate k p is determined in the simulation without of “steady-state” hypothesis. We explored the mechanism for the variation of polymerization kinetics those observed in previous studies, as well as polymerization-induced phase separation. Our Monte Carlo simulation scheme is versatile on studying polymerization kinetics in batch and semi-batch processes.

  5. Molecular Dynamics Simulations of Chemical Reactions for Use in Education

    Science.gov (United States)

    Qian Xie; Tinker, Robert

    2006-01-01

    One of the simulation engines of an open-source program called the Molecular Workbench, which can simulate thermodynamics of chemical reactions, is described. This type of real-time, interactive simulation and visualization of chemical reactions at the atomic scale could help students understand the connections between chemical reaction equations…

  6. Monte Carlo kinetics simulations of ice-mantle formation on interstellar grains

    Science.gov (United States)

    Garrod, Robin

    2015-08-01

    The majority of interstellar dust-grain chemical kinetics models use rate equations, or alternative population-based simulation methods, to trace the time-dependent formation of grain-surface molecules and ice mantles. Such methods are efficient, but are incapable of considering explicitly the morphologies of the dust grains, the structure of the ices formed thereon, or the influence of local surface composition on the chemistry.A new Monte Carlo chemical kinetics model, MIMICK, is presented here, whose prototype results were published recently (Garrod 2013, ApJ, 778, 158). The model calculates the strengths and positions of the potential mimima on the surface, on the fly, according to the individual pair-wise (van der Waals) bonds between surface species, allowing the structure of the ice to build up naturally as surface diffusion and chemistry occur. The prototype model considered contributions to a surface particle's potential only from contiguous (or "bonded") neighbors; the full model considers contributions from surface constituents from short to long range. Simulations are conducted on a fully 3-D user-generated dust-grain with amorphous surface characteristics. The chemical network has also been extended from the simple water system previously published, and now includes 33 chemical species and 55 reactions. This allows the major interstellar ice components to be simulated, such as water, methane, ammonia and methanol, as well as a small selection of more complex molecules, including methyl formate (HCOOCH3).The new model results indicate that the porosity of interstellar ices are dependent on multiple variables, including gas density, the dust temperature, and the relative accretion rates of key gas-phase species. The results presented also have implications for the formation of complex organic molecules on dust-grain surfaces at very low temperatures.

  7. 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)

  8. 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.

  9. Dynamic cardiac SPECT computer simulations for teboroxime kinetics

    International Nuclear Information System (INIS)

    A series of computer simulations was performed to examine the effect that each of seven factors have on the accuracy of the kinetic parameters (k21 and k12) of teboroxime (a 99mTc-labeled heart perfusion agent). The parameters k21 and k12 can be estimated using dynamic SPECT imaging and tracer kinetic modeling. The factors investigated were: (1) projection/reconstruction process of a time-varying tracer, (2) cardiac motion, (3) temporal resolution of the images, (4) attenuation effects, (5) emission statistics, (6) correlation of estimated parameters, and (7) decreased extraction fraction of teboroxime over time. The results showed that factors (3) and (6) affected only the %RMS error of the estimated parameters k21 and k12 and that the smallest error can be obtained by: using 5 second temporal resolution and selecting tissue ROIs which contain the least amount of intraventricular blood. Factors (2), (4), (5), and (7) significantly affected the accuracy of either k21 or k12 and efforts should be made in the future to either model or correct for these factors

  10. Simulation methods with extended stability for stiff biochemical Kinetics

    Directory of Open Access Journals (Sweden)

    Rué Pau

    2010-08-01

    Full Text Available Abstract Background With increasing computer power, simulating the dynamics of complex systems in chemistry and biology is becoming increasingly routine. The modelling of individual reactions in (biochemical systems involves a large number of random events that can be simulated by the stochastic simulation algorithm (SSA. The key quantity is the step size, or waiting time, τ, whose value inversely depends on the size of the propensities of the different channel reactions and which needs to be re-evaluated after every firing event. Such a discrete event simulation may be extremely expensive, in particular for stiff systems where τ can be very short due to the fast kinetics of some of the channel reactions. Several alternative methods have been put forward to increase the integration step size. The so-called τ-leap approach takes a larger step size by allowing all the reactions to fire, from a Poisson or Binomial distribution, within that step. Although the expected value for the different species in the reactive system is maintained with respect to more precise methods, the variance at steady state can suffer from large errors as τ grows. Results In this paper we extend Poisson τ-leap methods to a general class of Runge-Kutta (RK τ-leap methods. We show that with the proper selection of the coefficients, the variance of the extended τ-leap can be well-behaved, leading to significantly larger step sizes. Conclusions The benefit of adapting the extended method to the use of RK frameworks is clear in terms of speed of calculation, as the number of evaluations of the Poisson distribution is still one set per time step, as in the original τ-leap method. The approach paves the way to explore new multiscale methods to simulate (biochemical systems.

  11. Scaling of Ion Heating During Magnetic Reconnection: Kinetic PIC Simulations

    Science.gov (United States)

    Shay, M. A.; Haggerty, C. C.; McHugh, C.; Phan, T. D.; Drake, J. F.; Oieroset, M.

    2014-12-01

    Magnetic reconnection releases stored magnetic energy in the form of fast flows and heating, and plays an important role in many heliospheric and laboratory plasmas. There is still significant uncertainty as to the ultimate destination of the released magnetic energy, whether into bulk flows, thermal heating, or energetic particle production. Using a systematic set of 2D kinetic PIC simulations, we study how inflowing plasma conditions and the electron to ion mass ratio modifies the amount of ion heating during magnetic reconnection. Consistent with recent satellite observations, we find that the primary controlling factor is the inflowing Alfven speed, or the magnetic energy per electron-ion pair. In contrast with electron heating findings, introducing a guide field substantially reduces the amount of ion heating. Possible ion heating mechanisms, and well as relative electron to ion heating energy partition, will be discussed.

  12. Kinetic simulating experiment on the secondary hydrocarbon generation of kerogen

    Institute of Scientific and Technical Information of China (English)

    XIONG; Yongqiang

    2002-01-01

    [1]Magoon, L. B., Dow, W. G., The petroleum system, in The Petroleum System--from Source to Trap (eds., Magoon, L. B., Dow, W. G..), AAPG Memoir 60, 1994, 3-24.[2]Ungerer, P., Pelet, R., Extrapolation of oil and gas formation kinetics from laboratory experiments to sedimentary basins, Nature, 1987, 327: 52-54.[3]Behar, F., Kressmann, S., Vandenbroucke, M. et al., Experimental simulation in a confined system and kinetic modelling of kerogen and oil cracking, Org. Geochem., 1991, 19: 173-189.[4]Behar, F., Vandenbroucke, M., Tang, Y. et al., Thermal cracking of kerogen in open and closed systems: determination of kinetic parameters and stoichiometric coefficients for oil and gas generation, Org. Geochem, 1997, 26(5/6): 321-339.[5]Waples, D. W., Time and temperture in petroleum exploration: application of Lopatin's method to petroleum exploration, AAPG Bulletin, 1980, 64: 916-926.[6]Dai, H. M., Wang, S. Y., Wang, H. Q. et al., Formation characteristics of natural gas reservoirs and favorable exploration areas in Sinian-Cambrian, Petroleum Exploration and Development (in Chinese), 1999, 26(5): 16-20.[7]Editorial Committee of Petroleum Geology of China Petroleum, Petroleum Geology of China, Beijing: Petroleum Industry Press, 1989.[8]Liu, J. Z., Tang, Y. C., One example of predicting methane generation yield by hydrocarbon generating kinetics, Chinese Science Bulletin, 1998, 43(11): 1187-1191.[9]Wang, J., Huang, S. Y., Huang, G. S. et al., Basic Characteristics of the Earth's Temperature Distribution in China (in Chinese), Beijing: Seismological Press, 1990.[10]Wang, Y. G., Yu X. F., Yang Y. et al., Applications of fluid inclusions in the study of paleogeotemperature in Sichuan Basin, Earth Science--Journal of China University of Geosciences (in Chinese), 1998, 23(3): 285-288.[11]Wu, D. M., Wu, N. L., Gao, J. J., The study of paleogeotemperature in Shichuan Basin and their geological significance, Acta Petroleum Sinica (in

  13. 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...

  14. 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.

  15. Richardson Extrapolation Based Error Estimation for Stochastic Kinetic Plasma Simulations

    Science.gov (United States)

    Cartwright, Keigh

    2014-10-01

    To have a high degree of confidence in simulations one needs code verification, validation, solution verification and uncertainty qualification. This talk will focus on numerical error estimation for stochastic kinetic plasma simulations using the Particle-In-Cell (PIC) method and how it impacts the code verification and validation. A technique Is developed to determine the full converged solution with error bounds from the stochastic output of a Particle-In-Cell code with multiple convergence parameters (e.g. ?t, ?x, and macro particle weight). The core of this method is a multi parameter regression based on a second-order error convergence model with arbitrary convergence rates. Stochastic uncertainties in the data set are propagated through the model usin gstandard bootstrapping on a redundant data sets, while a suite of nine regression models introduces uncertainties in the fitting process. These techniques are demonstrated on Flasov-Poisson Child-Langmuir diode, relaxation of an electro distribution to a Maxwellian due to collisions and undriven sheaths and pre-sheaths. Sandia National Laboratories is a multie-program laboratory managed and operated by Sandia Corporation, a wholly owned subisidiary of Lockheed Martin Corporation, for the U.S. DOE's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

  16. Single Molecule Simulation of Diffusion and Enzyme Kinetics.

    Science.gov (United States)

    Pérez-Rodríguez, Gael; Gameiro, Denise; Pérez-Pérez, Martín; Lourenço, Anália; Azevedo, Nuno F

    2016-04-28

    This work presents a molecular-scale agent-based model for the simulation of enzymatic reactions at experimentally measured concentrations. The model incorporates stochasticity and spatial dependence, using diffusing and reacting particles with physical dimensions. We developed strategies to adjust and validate the enzymatic rates and diffusion coefficients to the information required by the computational agents, i.e., collision efficiency, interaction logic between agents, the time scale associated with interactions (e.g., kinetics), and agent velocity. Also, we tested the impact of molecular location (a source of biological noise) in the speed at which the reactions take place. Simulations were conducted for experimental data on the 2-hydroxymuconate tautomerase (EC 5.3.2.6, UniProt ID Q01468) and the Steroid Delta-isomerase (EC 5.3.3.1, UniProt ID P07445). Obtained results demonstrate that our approach is in accordance to existing experimental data and long-term biophysical and biochemical assumptions. PMID:27049044

  17. Atomistic computer simulations of FePt nanoparticles. Thermodynamic and kinetic properties

    Energy Technology Data Exchange (ETDEWEB)

    Mueller, M.

    2007-12-20

    In the present dissertation, a hierarchical multiscale approach for modeling FePt nanoparticles by atomistic computer simulations is developed. By describing the interatomic interactions on different levels of sophistication, various time and length scales can be accessed. Methods range from static quantum-mechanic total-energy calculations of small periodic systems to simulations of whole particles over an extended time by using simple lattice Hamiltonians. By employing these methods, the energetic and thermodynamic stability of non-crystalline multiply twinned FePt nanoparticles is investigated. Subsequently, the thermodynamics of the order-disorder transition in FePt nanoparticles is analyzed, including the influence of particle size, composition and modified surface energies by different chemical surroundings. In order to identify processes that reduce or enhance the rate of transformation from the disordered to the ordered state, the kinetics of the ordering transition in FePt nanoparticles is finally investigated by assessing the contributions of surface and volume diffusion. (orig.)

  18. 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

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

    Science.gov (United States)

    Srinivas, Niranjan

    hybridization, fraying, and branch migration, and provide a biophysical explanation of strand displacement kinetics. Our work paves the way for accurate modeling of strand displacement cascades, which would facilitate the simulation and construction of more complex molecular systems. In Chapters 3 and 4, we identify and overcome the crucial experimental challenges involved in using our general DNA-based technology for engineering dynamical behaviors in the test tube. In this process, we identify important design rules that inform our choice of molecular motifs and our algorithms for designing and verifying DNA sequences for our molecular implementation. We also develop flexible molecular strategies for "tuning" our reaction rates and stoichiometries in order to compensate for unavoidable non-idealities in the molecular implementation, such as imperfectly synthesized molecules and spurious "leak" pathways that compete with desired pathways. We successfully implement three distinct autocatalytic reactions, which we then combine into a de novo chemical oscillator. Unlike biological networks, which use sophisticated evolved molecules (like proteins) to realize such behavior, our test tube realization is the first to demonstrate that Watson-Crick base pairing interactions alone suffice for oscillatory dynamics. Since our design pipeline is general and applicable to any CRN, our experimental demonstration of a de novo chemical oscillator could enable the systematic construction of CRNs with other dynamic behaviors.

  20. 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...

  1. ε-Caprolactam migration from irradiated PA-6 food packaging: kinetic simulation and measurement

    International Nuclear Information System (INIS)

    Migration of low molecular mass compounds (LMMC), such as monomers and additives, from plastic packaging into food simulants is a very important issue, concerning public health and chemical contamination of foods. Sterilization of food packaging materials with ionizing radiation is considered an alternative to other sterilization methods, but when polymers are irradiated, LMMC may be formed, as radiolysis products. According to the Brazilian legislation, specific migration tests, such as those of LMMC from packaging into simulants, should be carried out at certain temperature and time, depending on the real conditions of contact. In this work, multilayer flexible films with polyamide 6 (PA-6), used for meat foodstuffs, were studied. The ε-caprolactam (PA-6 monomer) specific migration into acetic acid 3% simulant at 40 deg C during 10 days and at 100 deg C during 30 minutes was performed. The initial monomer level in the irradiated and non irradiated PA-6 films was quantified by high resolution gas chromatography (HRGC). Radiation doses were 3 and 7 kGy. ε-caprolactam specific migration was carried out only with non irradiated films. The results showed that radiation causes a significant change in the monomer level, up or down, depending on the multilayer film type. The kinetic of the ε-caprolactam migration at both temperatures, 40 and 100 deg C was clearly explained by the numerical simulation, combining an Arrhenius equation with the Fick's second law, although this kinetic was not experimentally studied. This simulation allowed to predict diffusion parameters estimates, like diffusion coefficients and activation energies of ε-caprolactam in the films or simulant. (author)

  2. 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.

  3. 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

  4. 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

  5. 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 ...

  6. 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...

  7. Study of knock in a high compression ratio SI methanol engine using LES with detailed chemical kinetics

    International Nuclear Information System (INIS)

    Highlights: • Knock in a high compression ratio spark ignition methanol engine was simulated. • We used LES coupled with detailed chemical kinetics to simulate knock. • OH radical was the predominant species during knocking combustion. • Weak species such as H2O2, CH2O, HO2 and HCO were also detected during knocking. • The stronger the reaction rate, the higher the knock intensity. - Abstract: Methanol as an alternative fuel is considered to be one of the most favorable fuels for internal combustion engines. In this paper, knock in a high compression ratio SI (Spark Ignition) methanol engine was studied by using LES (Large Eddy Simulation) coupled with detailed chemical kinetics. A 21-species, 84-reaction methanol reaction mechanism was adopted to simulate the auto-ignition and combustion process of the methanol/air mixture. The results showed that the end-gas auto-ignition first occurred in the place near the chamber wall because of the higher temperature and pressure. The evolution of OH radicals was essentially the same with the evolution of in-cylinder temperature. OH radicals could be a good temperature indicator. The concentration of HCO radicals was almost negligible during knocking combustion. There existed two effects for CH2O, OH, and H2O2, which were generation and consumption. The reaction intensities of CO, CH2O, H2O2, and OH species were higher than other species during knocking combustion

  8. Efficient Scheme for Chemical Flooding Simulation

    Directory of Open Access Journals (Sweden)

    Braconnier Benjamin

    2014-07-01

    Full Text Available In this paper, we investigate an efficient implicit scheme for the numerical simulation of chemical enhanced oil recovery technique for oil fields. For the sake of brevity, we only focus on flows with polymer to describe the physical and numerical models. In this framework, we consider a black oil model upgraded with the polymer modeling. We assume the polymer only transported in the water phase or adsorbed on the rock following a Langmuir isotherm. The polymer reduces the water phase mobility which can change drastically the behavior of water oil interfaces. Then, we propose a fractional step technique to resolve implicitly the system. The first step is devoted to the resolution of the black oil subsystem and the second to the polymer mass conservation. In such a way, jacobian matrices coming from the implicit formulation have a moderate size and preserve solvers efficiency. Nevertheless, the coupling between the black-oil subsystem and the polymer is not fully resolved. For efficiency and accuracy comparison, we propose an explicit scheme for the polymer for which large time step is prohibited due to its CFL (Courant-Friedrichs-Levy criterion and consequently approximates accurately the coupling. Numerical experiments with polymer are simulated : a core flood, a 5-spot reservoir with surfactant and ions and a 3D real case. Comparisons are performed between the polymer explicit and implicit scheme. They prove that our polymer implicit scheme is efficient, robust and resolves accurately the coupling physics. The development and the simulations have been performed with the software PumaFlow [PumaFlow (2013 Reference manual, release V600, Beicip Franlab].

  9. 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.

  10. 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

  11. Benchmark Simulations of Gyro-Kinetic Electron and Fully-Kinetic Ion Model for Lower Hybrid Waves in Linear Region

    International Nuclear Information System (INIS)

    Particle-in-cell (PIC) simulation method has been proved to be a good candidate to study the interactions between plasmas and radio-frequency waves. However, for waves in the lower hybrid range of frequencies, a full PIC simulation is not efficient due to its high computational cost. In this work, a gyro-kinetic electron and fully-kinetic ion (GeFi) particle simulation model is applied to study the propagations and mode conversion processes of lower hybrid waves (LHWs) in plasmas. With this method, the computational efficiency of LHW simulations is greatly increased by using a larger grid size and time step. The simulation results in the linear regime are validated by comparison with the linear theory. (magnetically confined plasma)

  12. 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

  13. 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.

  14. 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…

  15. Spectral Kinetic Simulation of the Ideal Multipole Resonance Probe

    Science.gov (United States)

    Gong, Junbo; Wilczek, Sebastian; Szeremley, Daniel; Oberrath, Jens; Eremin, Denis; Dobrygin, Wladislaw; Schilling, Christian; Friedrichs, Michael; Brinkmann, Ralf Peter

    2015-09-01

    The term Active Plasma Resonance Spectroscopy (APRS) denotes a class of diagnostic techniques which utilize the natural ability of plasmas to resonate on or near the electron plasma frequency ωpe: An RF signal in the GHz range is coupled into the plasma via an electric probe; the spectral response of the plasma is recorded, and a mathematical model is used to determine plasma parameters such as the electron density ne or the electron temperature Te. One particular realization of the method is the Multipole Resonance Probe (MRP). The ideal MRP is a geometrically simplified version of that probe; it consists of two dielectrically shielded, hemispherical electrodes to which the RF signal is applied. A particle-based numerical algorithm is described which enables a kinetic simulation of the interaction of the probe with the plasma. Similar to the well-known particle-in-cell (PIC), it contains of two modules, a particle pusher and a field solver. The Poisson solver determines, with the help of a truncated expansion into spherical harmonics, the new electric field at each particle position directly without invoking a numerical grid. The effort of the scheme scales linearly with the ensemble size N.

  16. Kinetic Monte Carlo Simulation of Oxygen Diffusion in Ytterbium Disilicate

    Science.gov (United States)

    Good, Brian S.

    2015-01-01

    Silicon-based ceramic components for next-generation jet turbine engines offer potential weight savings, as well as higher operating temperatures, both of which lead to increased efficiency and lower fuel costs. Silicon carbide (SiC), in particular, offers low density, good strength at high temperatures, and good oxidation resistance in dry air. However, reaction of SiC with high-temperature water vapor, as found in the hot section of jet turbine engines in operation, can cause rapid surface recession, which limits the lifetime of such components. Environmental Barrier Coatings (EBCs) are therefore needed if long component lifetime is to be achieved. Rare earth silicates such as Yb2Si2O7 and Yb2SiO5 have been proposed for such applications; in an effort to better understand diffusion in such materials, we have performed kinetic Monte Carlo (kMC) simulations of oxygen diffusion in Ytterbium disilicate, Yb2- Si2O7. The diffusive process is assumed to take place via the thermally activated hopping of oxygen atoms among oxygen vacancy sites or among interstitial sites. Migration barrier energies are computed using density functional theory (DFT).

  17. Kinetic Monte Carlo Simulation of Oxygen Diffusion in Ytterbium Disilicate

    Science.gov (United States)

    Good, Brian S.

    2015-01-01

    Ytterbium disilicate is of interest as a potential environmental barrier coating for aerospace applications, notably for use in next generation jet turbine engines. In such applications, the transport of oxygen and water vapor through these coatings to the ceramic substrate is undesirable if high temperature oxidation is to be avoided. In an effort to understand the diffusion process in these materials, we have performed kinetic Monte Carlo simulations of vacancy-mediated and interstitial oxygen diffusion in Ytterbium disilicate. Oxygen vacancy and interstitial site energies, vacancy and interstitial formation energies, and migration barrier energies were computed using Density Functional Theory. We have found that, in the case of vacancy-mediated diffusion, many potential diffusion paths involve large barrier energies, but some paths have barrier energies smaller than one electron volt. However, computed vacancy formation energies suggest that the intrinsic vacancy concentration is small. In the case of interstitial diffusion, migration barrier energies are typically around one electron volt, but the interstitial defect formation energies are positive, with the result that the disilicate is unlikely to exhibit experience significant oxygen permeability except at very high temperature.

  18. The decay kinetics of residual chlorine in cooling seawater simulation experiments

    Institute of Scientific and Technical Information of China (English)

    ZENG Jiangning; JIANG Zhibing; CHEN Quanzhen; ZHENG Ping; HUANG Yijun

    2009-01-01

    To find out the decay character of residual chlorine (RC) in the sea water, the concentration of RC was analyzed by N, N-diethyl-p-phenylenediamine (DPD) method under different simulation experimental conditions, in which salinity, temperature, and Chemical Oxygen Demand (COD) were selected. The water used in the experiment was the mixture of aging ocean water, coastal water and extracting solution of coastal sediment at appropriate level. Results are shown as follows: (1)Piecewise function can well reflect the decay dynamics of RC in the cooling seawater. Concretely,the decay dynamics of first 1 min is too rapid to ascertain using a specific kinetic function, and that of the time from 1 to 30 min is fit for the first-order kinetic model. (2) The results could be the foundation of the chemical behavior of RC in seawater, and be used as not only the guidance of the coastal power plants production and sea water desalting companies, but also the establishment of the correlative trade standard.

  19. 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.

  20. 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

  1. 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.)

  2. Kinetics of chemical vapor deposition of boron on molybdenum

    International Nuclear Information System (INIS)

    Experimental rate data of chemical vapor deposition of boron by reduction of boron trichloride with hydrogen are analyzed to determine the reaction mechanism. The experiments were conducted at atmospheric pressure. The weight change of the sample was noted by means of a thermobalance. Molybdenum was used as the substrate. It has been found that the outer layer of the deposited film is Mo/sub 2/B/sub 5/ and the inner layer is MoB, and in the stational state of the reaction, the diffusion in the solid state is considered not to be rate controlling. When mass transport limitation was absent, the reaction orders with respect to boron trichloride and hydrogen were one third and one half, respectively. By comparing these orders with those obtained from Langmuir-Hinshelwood type equations, the rate controlling mechanism is identified to be the desorption of hydrogen chloride from the substrate

  3. 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.

  4. 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...

  5. Kinetics programs for simulation of tropospheric photochemistry on the global scale

    International Nuclear Information System (INIS)

    The study of tropospheric kinetics underlies global change because key greenhouse gases are photochemically active. Modeling of tropospheric chemistry on a global scale is essential because some indirect greenhouse gases are short-lived and interact in a non-linear fashion. It is also extremely challenging, however; the global change grid is extensive in both the physical and temporal domains, and critical lower atmospheric species include the organics and their oxidized derivatives, which are numerous. Several types of optimization may be incorporated into kinetics modules to enhance their ability to simulate the complete lower atmospheric gas phase chemical system. (1) The photochemical integrator can be accelerated by avoiding matrix and iterative solutions and by establishing families. Accuracy and mass conservation are sacrificed in the absence of iteration, but atom balancing is restorable post hoc. (2) Chemistry can be arranged upon the massive grid to exploit parallel processing, and solutions to its continuity equations can be automated to permit experimentation with species and reaction lists or family definitions. Costs in programming effort will be incurred in these cases. (3) Complex hydrocarbon decay sequences can be streamlined either through structural lumping methods descended from smog investigations, which require considerable calibration, or by defining surrogates for classes of compounds, with a loss in constituent detail. From among the available options, the most advantageous permutations will vary with the specific nature of any eventual global scale study, and there is likely to be demand for many approaches. Tracer transport codes serve as a foundation upon which tropospheric chemistry packages will be tested. Encroachment of the NOx sphere of influence upon tropical rain forests and the upper free troposphere are two examples of specific problems to which full three-dimensional chemical simulations might be applied

  6. Stochastic linear multistep methods for the simulation of chemical kinetics

    International Nuclear Information System (INIS)

    In this paper, we introduce the Stochastic Adams-Bashforth (SAB) and Stochastic Adams-Moulton (SAM) methods as an extension of the τ-leaping framework to past information. Using the Θ-trapezoidal τ-leap method of weak order two as a starting procedure, we show that the k-step SAB method with k ≥ 3 is order three in the mean and correlation, while a predictor-corrector implementation of the SAM method is weak order three in the mean but only order one in the correlation. These convergence results have been derived analytically for linear problems and successfully tested numerically for both linear and non-linear systems. A series of additional examples have been implemented in order to demonstrate the efficacy of this approach

  7. Stochastic linear multistep methods for the simulation of chemical kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Barrio, Manuel, E-mail: mbarrio@infor.uva.es [Departamento de Informática, University of Valladolid, Valladolid (Spain); Burrage, Kevin [Department of Computer Science, University of Oxford, Oxford (United Kingdom); School of Mathematical Sciences, Queensland University of Technology, Brisbane (Australia); Burrage, Pamela [School of Mathematical Sciences, Queensland University of Technology, Brisbane (Australia)

    2015-02-14

    In this paper, we introduce the Stochastic Adams-Bashforth (SAB) and Stochastic Adams-Moulton (SAM) methods as an extension of the τ-leaping framework to past information. Using the Θ-trapezoidal τ-leap method of weak order two as a starting procedure, we show that the k-step SAB method with k ≥ 3 is order three in the mean and correlation, while a predictor-corrector implementation of the SAM method is weak order three in the mean but only order one in the correlation. These convergence results have been derived analytically for linear problems and successfully tested numerically for both linear and non-linear systems. A series of additional examples have been implemented in order to demonstrate the efficacy of this approach.

  8. Kinetically constrained ring-polymer molecular dynamics for non-adiabatic chemical reactions

    International Nuclear Information System (INIS)

    We extend ring-polymer molecular dynamics (RPMD) to allow for the direct simulation of general, electronically non-adiabatic chemical processes. The kinetically constrained (KC) RPMD method uses the imaginary-time path-integral representation in the set of nuclear coordinates and electronic states to provide continuous equations of motion that describe the quantized, electronically non-adiabatic dynamics of the system. KC-RPMD preserves the favorable properties of the usual RPMD formulation in the position representation, including rigorous detailed balance, time-reversal symmetry, and invariance of reaction rate calculations to the choice of dividing surface. However, the new method overcomes significant shortcomings of position-representation RPMD by enabling the description of non-adiabatic transitions between states associated with general, many-electron wavefunctions and by accurately describing deep-tunneling processes across asymmetric barriers. We demonstrate that KC-RPMD yields excellent numerical results for a range of model systems, including a simple avoided-crossing reaction and condensed-phase electron-transfer reactions across multiple regimes for the electronic coupling and thermodynamic driving force

  9. Kinetically constrained ring-polymer molecular dynamics for non-adiabatic chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Menzeleev, Artur R.; Bell, Franziska; Miller, Thomas F., E-mail: tfm@caltech.edu [Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125 (United States)

    2014-02-14

    We extend ring-polymer molecular dynamics (RPMD) to allow for the direct simulation of general, electronically non-adiabatic chemical processes. The kinetically constrained (KC) RPMD method uses the imaginary-time path-integral representation in the set of nuclear coordinates and electronic states to provide continuous equations of motion that describe the quantized, electronically non-adiabatic dynamics of the system. KC-RPMD preserves the favorable properties of the usual RPMD formulation in the position representation, including rigorous detailed balance, time-reversal symmetry, and invariance of reaction rate calculations to the choice of dividing surface. However, the new method overcomes significant shortcomings of position-representation RPMD by enabling the description of non-adiabatic transitions between states associated with general, many-electron wavefunctions and by accurately describing deep-tunneling processes across asymmetric barriers. We demonstrate that KC-RPMD yields excellent numerical results for a range of model systems, including a simple avoided-crossing reaction and condensed-phase electron-transfer reactions across multiple regimes for the electronic coupling and thermodynamic driving force.

  10. Interactions of multiphase hydrodynamics, droplet evaporation, and chemical kinetics in FCC riser reactors.

    Energy Technology Data Exchange (ETDEWEB)

    Chang, S. L.

    1998-02-17

    A computational fluid dynamics (CFD) computer code, ICRKFLO, has been developed for flow simulation of fluid catalytic cracking (FCC) riser reactors, which convert crude oil into gasoline and other valuable products. The FCC flow, especially in the entry region, is a three-phase reacting flow including hot catalyst particles, inert lift gas, and feed oil droplets. The impact of the hydrodynamics processes of heat transfer, droplet evaporation, and mixing on the chemical kinetics or riser performance can be significant. ICRKFLO was used to evaluate the impact of these processes on the performance of an advanced FCC unit. The code solves for major flow properties of all three phases in an FCC riser, with models governing the transport of catalyst particles and feed oil droplet, the vaporization of the feed oil droplets, the cracking of the oil vapor, and the formation and deposition of coke on particles. First, the code was validated against available test data of a pilot-scale FCC unit. Then, flow calculations for the FCC unit were performed. Computational results indicate that the heat transfer and droplet vaporization processes have a significant impact on the performance of a pilot-scale FCC unit. The impact is expected to be even greater on commercial scale units.

  11. 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...

  12. 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

  13. 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.

  14. 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...

  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

    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. 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…

  17. 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...

  18. 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…

  19. 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

  20. 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.

  1. 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

  2. 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…

  3. Computer simulation of crystallization kinetics with non-Poisson distributed nuclei

    OpenAIRE

    Uebele, Patric; Hermann, Helmut

    1996-01-01

    The influence of non-uniform distribution of nuclei on crystallization kinetics of amorphous materials is investigated. This case cannot be described by the well-known Johnson-Mehl-Avrami (JMA) equation, which is only valid under the assumption of a spatially homogeneous nucleation probability. The results of computer simulations of crystallization kinetics with nuclei distributed according to a cluster and a hardcore distribution are compared with JMA kinetics. The effects of the different d...

  4. 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

  5. Treatment of simulated odor from RDF plant using ashumale kinetic modelling

    International Nuclear Information System (INIS)

    The impact of ambient odour in the vicinity of the Semenyih MSW processing plant, commonly known as RDF plant, can be very negative to the nearby population, causing public restlessness and consequently affecting the business operation and sustain ability of the plant. The precise source of the odour, types, emission level and the meteorological conditions are needed to predict and established the ambient odour level at the perimeter fence of the plant and address it with respect to the ambient standards. To develop the odour gas model for the purpose of treatment is very compulsory because in MSW odour it contain many component of chemical that contribute the smell. Upon modelling using an established package as well as site measurements, the odour level at the perimeter fence of the plant was deduced and found to be marginally high, above the normal ambient level. Based on this issue, a study was made to evaluate the possibility of treating odour using Electron Beam Process. This paper will address and discuss the measurement of ambient concentration of three chemical components of the odour, namely benzene, dimethyl sulfide and trimethyl amine, the dispersion modeling to establish the critical ambient emission level, as well as and kinetic modeling of the treatment process and its experimental validation using a simulated odour. The focus will be made on exploring the use of Ashmuli kinetic modeling to develop correlations between the odour concentrations, odour chemical compositions and electron beam dose with the treatment efficiency, as well as adapting the model for MSW odour controls. (author)

  6. Phase IV Simulant Testing of Monosodium Titanate Adsorption Kinetics

    International Nuclear Information System (INIS)

    The Salt Disposition Systems Engineering Team identified the adsorption kinetics of actinides and strontium onto monosodium titanate (MST) as a technical risk in several of the processing alternatives selected for additional evaluation in Phase III of their effort

  7. Experiences on dynamic simulation software in chemical engineering education

    DEFF Research Database (Denmark)

    Komulainen, Tiina M.; Enemark-rasmussen, Rasmus; Sin, Gürkan;

    2012-01-01

    Commercial process simulators are increasing interest in the chemical engineer education. In this paper, the use of commercial dynamic simulation software, D-SPICE® and K-Spice®, for three different chemical engineering courses is described and discussed. The courses cover the following topics......: basic chemical engineering, operability and safety analysis and process control. User experiences from both teachers and students are presented. The benefits of dynamic simulation as an additional teaching tool are discussed and summarized. The experiences confirm that commercial dynamic simulators...... provide realistic training and can be successfully integrated into undergraduate and graduate teaching, laboratory courses and research....

  8. Chemical Kinetic Modeling of Dimethyl Carbonate in an Opposed-Flow Diffusion Flame

    Energy Technology Data Exchange (ETDEWEB)

    Glaude, P A; Pitz, W J; Thomson, M J

    2003-12-08

    Dimethyl carbonate (DMC) has been of interest as an oxygenate additive to diesel fuel because of its high oxygen content. In this study, a chemical kinetic mechanism for DMC was developed for the first time and used to understand its combustion under conditions in an opposed flow diffusion flame. Computed results were compared to experimental results from an opposed flow diffusion flame. It was found that the decomposition rate DMC {yields} H{sub 3}COC(=O)O. + CH{sub 3} in the flame was much slower than originally thought because resonance stabilization in the H{sub 3}COC(=O)O. radical was less than expected. Also, a new molecular elimination path for DMC is proposed and its rate calculated by quantum chemical methods. In the simulations of DMC in the flame, it was determined that much of the oxygen in dimethyl carbonate goes directly to CO{sub 2}. This characteristic indicates that DMC would not be an effective oxygenate additive for reducing soot emissions from diesel engines. In an ideal oxygenate additive for diesel fuel, each oxygen atom stays bonded to one carbon atom in the products thereby preventing the formation of carbon-carbon bonds that can lead to soot. When CO2 is formed directly, two oxygen atoms are bonded to one carbon atom thereby wasting one oxygen atom in the oxygenate additive. To determine how much CO{sub 2} is formed directly, the branching ratio of the key reaction, CH{sub 3}OC.=O going to the products CH{sub 3} + CO{sub 2} or CH{sub 3}O + CO was determined by ab initio methods. The A-factors of the rate constant of this reaction were found to be about 20 times higher than previous factors estimates. The new reaction rate constants obtained can be used as reaction rate rules for all oxygenates that contain the ester moiety including biodiesel.

  9. Galaxy Formation and Chemical Evolution in Hierarchical Hydrodynamical Simulations

    OpenAIRE

    Cora, S. A.; Mosconi, M. B.; P. B. Tissera; Lambas, D. G.

    2000-01-01

    We report first results of an implementation of a chemical model in a cosmological code, based on the Smoothed Particle Hydrodynamics (SPH) technique. We show that chemical SPH simulations are a promising tool to provide clues for the understanding of the chemical properties of galaxies in relation to their formation and evolution in a cosmological framework.

  10. Structure of kinetic/non-kinetic scale velocity shear layers and associated Kelvin-Helmholtz vortices: particle simulations

    Science.gov (United States)

    Nakamura, T.; Hasegawa, H.; Shinohara, I.

    2009-12-01

    Recent in-situ observations have revealed that Kelvin-Helmholtz (KH) vortices can roll-up not only at the Earth's magnetopause but also at the Mercury's magnetopause. Since kinetic effects cannot be neglected in Mercury-like small-scale situations, to universally understand the structure of the KH vortex the kinetic effects should be considered. Thus, in this study, we have performed 2D full particle (EM-PIC) simulations of KH vortices arising from kinetic and non-kinetic scale velocity shear layers. In this study, we focus on the basic situation in which the initial density, temperature and magnetic field are uniform and the magnetic field is perpendicular to the k-vector of KH instability. First, we investigated the kinetic equilibrium of velocity shear layers. In our simulation settings, particles are initialized with shifted Maxwellian velocity distributions having a bulk flow Vx0=±V0*tanh(Y/D0), where D0 is the initial half thickness of the velocity shear layer and V0 is the initial velocity jump across the shear layer. The +V0 (-V0) case corresponds to the dawn (dusk) case of the Earth’s and Mercury's situations. The Maxwellian loading of the particles, however, is only an approximation of equilibrium conditions, and past kinetic studies have shown that the true equilibrium condition is affected by the ion gyro-motion especially when D0dusk) case becomes thicker (thinner) as V0/Vthi increases, where Vthi is the ion thermal speed. This is because gyro-radii of ions which cross the boundary become larger (smaller) by the outward (inward) convection electric field in the dawn (dusk) case. Next, we investigated the evolution process of the KHI arising from kinetic and non-kinetic scale velocity shear layers. We first found that the linear growth rates of KHI are not affected by kinetic effects even when D0dusk) case is larger (smaller) than the electron rotation speed. This result can be explained by the centrifugal drift for ions; since the directions of the

  11. 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.

  12. Minimal Curvature Trajectories: Riemannian Geometry Concepts for Model Reduction in Chemical Kinetics

    CERN Document Server

    Lebiedz, Dirk; Siehr, Jochen

    2009-01-01

    In dissipative ordinary differential equation systems different time scales cause anisotropic phase volume contraction along solution trajectories. Model reduction methods exploit this for simplifying chemical kinetics via a time scale separation into fast and slow modes. The aim is to approximate the system dynamics with a dimension-reduced model after eliminating the fast modes by enslaving them to the slow ones via computation of a slow attracting manifold. We present a novel method for computing approximations of such manifolds using trajectory-based optimization. We discuss Riemannian geometry concepts as a basis for suitable optimization criteria characterizing trajectories near slow attracting manifolds and thus provide insight into fundamental geometric properties of multiple time scale chemical kinetics. The optimization criteria correspond to a suitable mathematical formulation of "minimal relaxation" of chemical forces along reaction trajectories under given constraints. We present various geometri...

  13. Multiscale GasKinetics/Particle (MGP) Simulation for Rocket Plume/Lunar Dust Interactions Project

    Data.gov (United States)

    National Aeronautics and Space Administration — A Multiscale GasKinetic/Particle (MGP) computational method is proposed to simulate the plume-crater-interaction/dust-impingement(PCIDI) problem. The MGP method...

  14. 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.

  15. Simulation of chemical reaction dynamics on an NMR quantum computer

    CERN Document Server

    Lu, Dawei; Xu, Ruixue; Chen, Hongwei; Gong, Jiangbin; Peng, Xinhua; Du, Jiangfeng

    2011-01-01

    Quantum simulation can beat current classical computers with minimally a few tens of qubits and will likely become the first practical use of a quantum computer. One promising application of quantum simulation is to attack challenging quantum chemistry problems. Here we report an experimental demonstration that a small nuclear-magnetic-resonance (NMR) quantum computer is already able to simulate the dynamics of a prototype chemical reaction. The experimental results agree well with classical simulations. We conclude that the quantum simulation of chemical reaction dynamics not computable on current classical computers is feasible in the near future.

  16. Kinetic lattice Monte-Carlo simulations on the ordering kinetics of free and supported FePt L10-nanoparticles

    Directory of Open Access Journals (Sweden)

    Michael Müller

    2011-01-01

    Full Text Available The ordering kinetics in free and supported L10 nanoparticles was studied by means of lattice-based kinetic Monte-Carlo simulations. Starting from a fully disordered particle of Wulff shape, the simulations show that the nucleation of ordered domains is starting quickly on various (100 facets but is retarded in the particle volume due to the lack of vacancies compared with a thin film geometry. If a substrate is present, we do not find significant differences in the ordering behavior. This holds true, even if we impose a massively increased thermodynamic driving force for interface segregation, because the nucleation of ordered domains on free facets is significantly faster than the bulk diffusion of the segregating species to the interface. In cases where wetting of the substrate or surface facetting occurs, we find that diffusional atomic motion on the surface goes along with an enhanced long-range order.

  17. Evaluation of the interindividual human variation in bioactivation of methyleugenol using physiologically based kinetic modeling and Monte Carlo simulations

    Energy Technology Data Exchange (ETDEWEB)

    Al-Subeihi, Ala' A.A., E-mail: subeihi@yahoo.com [Division of Toxicology, Wageningen University, Tuinlaan 5, 6703 HE Wageningen (Netherlands); BEN-HAYYAN-Aqaba International Laboratories, Aqaba Special Economic Zone Authority (ASEZA), P. O. Box 2565, Aqaba 77110 (Jordan); Alhusainy, Wasma; Kiwamoto, Reiko; Spenkelink, Bert [Division of Toxicology, Wageningen University, Tuinlaan 5, 6703 HE Wageningen (Netherlands); Bladeren, Peter J. van [Division of Toxicology, Wageningen University, Tuinlaan 5, 6703 HE Wageningen (Netherlands); Nestec S.A., Avenue Nestlé 55, 1800 Vevey (Switzerland); Rietjens, Ivonne M.C.M.; Punt, Ans [Division of Toxicology, Wageningen University, Tuinlaan 5, 6703 HE Wageningen (Netherlands)

    2015-03-01

    The present study aims at predicting the level of formation of the ultimate carcinogenic metabolite of methyleugenol, 1′-sulfooxymethyleugenol, in the human population by taking variability in key bioactivation and detoxification reactions into account using Monte Carlo simulations. Depending on the metabolic route, variation was simulated based on kinetic constants obtained from incubations with a range of individual human liver fractions or by combining kinetic constants obtained for specific isoenzymes with literature reported human variation in the activity of these enzymes. The results of the study indicate that formation of 1′-sulfooxymethyleugenol is predominantly affected by variation in i) P450 1A2-catalyzed bioactivation of methyleugenol to 1′-hydroxymethyleugenol, ii) P450 2B6-catalyzed epoxidation of methyleugenol, iii) the apparent kinetic constants for oxidation of 1′-hydroxymethyleugenol, and iv) the apparent kinetic constants for sulfation of 1′-hydroxymethyleugenol. Based on the Monte Carlo simulations a so-called chemical-specific adjustment factor (CSAF) for intraspecies variation could be derived by dividing different percentiles by the 50th percentile of the predicted population distribution for 1′-sulfooxymethyleugenol formation. The obtained CSAF value at the 90th percentile was 3.2, indicating that the default uncertainty factor of 3.16 for human variability in kinetics may adequately cover the variation within 90% of the population. Covering 99% of the population requires a larger uncertainty factor of 6.4. In conclusion, the results showed that adequate predictions on interindividual human variation can be made with Monte Carlo-based PBK modeling. For methyleugenol this variation was observed to be in line with the default variation generally assumed in risk assessment. - Highlights: • Interindividual human differences in methyleugenol bioactivation were simulated. • This was done using in vitro incubations, PBK modeling

  18. Evaluation of the interindividual human variation in bioactivation of methyleugenol using physiologically based kinetic modeling and Monte Carlo simulations

    International Nuclear Information System (INIS)

    The present study aims at predicting the level of formation of the ultimate carcinogenic metabolite of methyleugenol, 1′-sulfooxymethyleugenol, in the human population by taking variability in key bioactivation and detoxification reactions into account using Monte Carlo simulations. Depending on the metabolic route, variation was simulated based on kinetic constants obtained from incubations with a range of individual human liver fractions or by combining kinetic constants obtained for specific isoenzymes with literature reported human variation in the activity of these enzymes. The results of the study indicate that formation of 1′-sulfooxymethyleugenol is predominantly affected by variation in i) P450 1A2-catalyzed bioactivation of methyleugenol to 1′-hydroxymethyleugenol, ii) P450 2B6-catalyzed epoxidation of methyleugenol, iii) the apparent kinetic constants for oxidation of 1′-hydroxymethyleugenol, and iv) the apparent kinetic constants for sulfation of 1′-hydroxymethyleugenol. Based on the Monte Carlo simulations a so-called chemical-specific adjustment factor (CSAF) for intraspecies variation could be derived by dividing different percentiles by the 50th percentile of the predicted population distribution for 1′-sulfooxymethyleugenol formation. The obtained CSAF value at the 90th percentile was 3.2, indicating that the default uncertainty factor of 3.16 for human variability in kinetics may adequately cover the variation within 90% of the population. Covering 99% of the population requires a larger uncertainty factor of 6.4. In conclusion, the results showed that adequate predictions on interindividual human variation can be made with Monte Carlo-based PBK modeling. For methyleugenol this variation was observed to be in line with the default variation generally assumed in risk assessment. - Highlights: • Interindividual human differences in methyleugenol bioactivation were simulated. • This was done using in vitro incubations, PBK modeling

  19. Kinetic simulation of direct-drive capsule implosions and its comparison with experiments and radiation hydrodynamic simulation

    Science.gov (United States)

    Kwan, Thomas; Le, Ari; Schmitt, Mark; Herrmann, Hans; Batha, Steve

    2015-11-01

    We have carried out simulations of direct-drive capsule implosion experiments conducted on Omega laser facility at the Laboratory of Laser energetics of the University of Rochester. The capsules had a glass shell (SiO2) with D, T, He-3 fills at various proportions. One-dimensional radiation hydrodynamic calculations and kinetic particle/hybrid simulations with LSP were carried out for the post-shot analysis to compare neutron yield, yield ratio, and shell convergence in assessing the effects of plasma kinetic effects. The LSP simulations were initiated with the output from the rad-hydro simulations at the end of the laser-drive. The electrons are treated as a fluid while all the ion species by the kinetic PIC technique. Our LSP simulations clearly showed species separation between the deuterons, tritons and He-3 during the implosion but significantly less after the compression. The neutron yield, gamma bang-time and -width from the LSP simulations compared favorably with experiments. Detail comparison among the kinetic simulations, rad-hydro simulations, and experimental results will be presented. Work performed under the auspices of the US Department of Energy by Los Alamos National Laboratory under Contract No. W-7405-ENG-36.

  20. 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.

  1. VPPD Lab - The Chemical Product Simulator

    DEFF Research Database (Denmark)

    Kalakul, Sawitree; Hussain, Rehan; Elbashir, Nimir;

    2015-01-01

    , detergent, etc.). It has interface to identify workflow/data-flow for the inter-related activities between knowledge-based system and model-based calculation procedures to systematically, efficiently and robustly solve various types of product design-analysis problems. The application of the software is......In this paper, the development of a systematic model-based framework for product design, implemented in the new product design software called VPPD-Lab is presented. This framework employs its in-house knowledge-based system to design and evaluate chemical products. The built-in libraries of...... product performance models and product-chemical property models are used to evaluate different classes of product. The product classes are single molecular structure chemicals (lipids, solvents, aroma, etc.), blended products (gasoline, jet-fuels, lubricants, etc.), and emulsified product (hand wash...

  2. Research in chemical kinetics: Progress report, January 1, 1978-September 30, 1978

    International Nuclear Information System (INIS)

    Research was conducted on the following topics: stratospheric chemistry of chlorinated molecules, atmospheric chemistry of methane, atmospheric chemistry of cosmogenic tritium, reactions of energetic and thermal radioactive atoms, methylene chemistry, and laboratory simulation of chemical reactions in Jupiter atmosphere

  3. Research in Chemical Kinetics: Progress Report, January 1, 1978 to September 30, 1978

    Science.gov (United States)

    Rowland, F. S.

    1978-01-01

    Research was conducted on the following topics: stratospheric chemistry of chlorinated molecules, atmospheric chemistry of methane, atmospheric chemistry of cosmogenic tritium, reactions of energetic and thermal radioactive atoms, methylene chemistry, and laboratory simulation of chemical reactions in Jupiter atmosphere. (DLC)

  4. 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...

  5. 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

  6. Simulations of the anisotropic kinetic and magnetic alpha effects

    CERN Document Server

    Brandenburg, A

    2007-01-01

    The validity of a closure called the minimal tau approximation (MTA), is tested in the context of dynamo theory, wherein triple correlations are assumed to provide relaxation of the turbulent electromotive force. Under MTA, the alpha effect in mean field dynamo theory becomes proportional to a relaxation time scale multiplied by the difference between kinetic and current helicities. It is shown that the value of the relaxation time is positive and, in units of the turnover time at the forcing wavenumber, it is of the order of unity. It is quenched by the magnetic field -- roughly independently of the magnetic Reynolds number. However, this independence becomes uncertain at large magnetic Reynolds number. Kinetic and current helicities are shown to be dominated by large scale properties of the flow.

  7. 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.

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

    OpenAIRE

    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...

  9. 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...

  10. 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...

  11. 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.

  12. 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 ...

  13. A chemical EOR benchmark study of different reservoir simulators

    Science.gov (United States)

    Goudarzi, Ali; Delshad, Mojdeh; Sepehrnoori, Kamy

    2016-09-01

    Interest in chemical EOR processes has intensified in recent years due to the advancements in chemical formulations and injection techniques. Injecting Polymer (P), surfactant/polymer (SP), and alkaline/surfactant/polymer (ASP) are techniques for improving sweep and displacement efficiencies with the aim of improving oil production in both secondary and tertiary floods. There has been great interest in chemical flooding recently for different challenging situations. These include high temperature reservoirs, formations with extreme salinity and hardness, naturally fractured carbonates, and sandstone reservoirs with heavy and viscous crude oils. More oil reservoirs are reaching maturity where secondary polymer floods and tertiary surfactant methods have become increasingly important. This significance has added to the industry's interest in using reservoir simulators as tools for reservoir evaluation and management to minimize costs and increase the process efficiency. Reservoir simulators with special features are needed to represent coupled chemical and physical processes present in chemical EOR processes. The simulators need to be first validated against well controlled lab and pilot scale experiments to reliably predict the full field implementations. The available data from laboratory scale include 1) phase behavior and rheological data; and 2) results of secondary and tertiary coreflood experiments for P, SP, and ASP floods under reservoir conditions, i.e. chemical retentions, pressure drop, and oil recovery. Data collected from corefloods are used as benchmark tests comparing numerical reservoir simulators with chemical EOR modeling capabilities such as STARS of CMG, ECLIPSE-100 of Schlumberger, REVEAL of Petroleum Experts. The research UTCHEM simulator from The University of Texas at Austin is also included since it has been the benchmark for chemical flooding simulation for over 25 years. The results of this benchmark comparison will be utilized to improve

  14. Kinetic simulation of rarefied and weakly ionized hypersonic flow fields

    Science.gov (United States)

    Farbar, Erin D.

    When a vehicle enters the Earth's atmosphere at the very large velocities associated with Lunar and Mars return, a strong bow shock is formed in front of the vehicle. The shock heats the air to very high temperatures, causing collisions that are sufficiently energetic to produce ionized particles. As a result, a weakly ionized plasma is formed in the region between the bow shock and the vehicle surface. The presence of this plasma impedes the transport of radio frequency waves to the vehicle, causing the phenomenon known as "communications black out". The plasma also interacts with the neutral particles in the flow field, and contributes to the heat flux at the vehicle surface. Since it is difficult to characterize these flow fields using flight or ground based experiments, computational tools play an important role in the design of reentry vehicles. It is important to include the physical phenomena associated with the presence of the plasma in the computational analysis of the flow fields about these vehicles. Physical models for the plasma phenomena are investigated using a state of the art, Direct Simulation Monte Carlo (DSMC) code. Models for collisions between charged particles, plasma chemistry, and the self-induced electric field that currently exist in the literature are implemented. Using these baseline models, steady state flow field solutions are computed for the FIRE II reentry vehicle at two different trajectory points. The accuracy of each baseline plasma model is assessed in a systematic fashion, using one flight condition of the FIRE II vehicle as the test case. Experimental collision cross section data is implemented to model collisions of electrons with neutral particles. Theoretical and experimental reaction cross section data are implemented to model chemical reactions that involve electron impact, and an associative ionization reaction. One-dimensional Particle-In-Cell (PIC) routines are developed and coupled to the DSMC code, to assess the

  15. Molecular kinetic theory of boundary slip on textured surfaces by molecular dynamics simulations

    Institute of Scientific and Technical Information of China (English)

    WANG LiYa; WANG FengChao; YANG FuQian; WU HengAn

    2014-01-01

    A theoretical model extended from the Frenkel-Eyring molecular kinetic theory (MKT) was applied to describe the boundary slip on textured surfaces.The concept of the equivalent depth of potential well was adopted to characterize the solid-liquid interactions on the textured surfaces.The slip behaviors on both chemically and topographically textured surfaces were investigated using molecular dynamics (MD) simulations.The extended MKT slip model is validated by our MD simulations under various situations,by constructing different complex surfaces and varying the surface wettability as well as the shear stress exerted on the liquid.This slip model can provide more comprehensive understanding of the liquid flow on atomic scale by considering the influence of the solid-liquid interactions and the applied shear stress on the nano-flow.Moreover,the slip velocity shear-rate dependence can be predicted using this slip model,since the nonlinear increase of the slip velocity under high shear stress can be approximated by a hyperbolic sine function.

  16. Anaerobic digestion of buffalo dung: simulation of process kinetics

    International Nuclear Information System (INIS)

    Assessment of kinetic of AD (Anaerobic Digestion) is a beneficial practice to forecast the performance of the process. It is helpful in the design of AD vessels, substrate feeding and digestate exit systems. The aim of this work was to assess the kinetics of anaerobically digested buffalo dung at different quantities of water added. It comprises the assessment of the specific methane production on the basis of VS (Volatile Solids) added in each reactor by using three first order models, i.e. the modified Gompertz model, the Cone model and the Exponential Curve Factor model. The analysis was tested by using the three statistical parameters, i.e. the coefficient of multiple determinations, the standard deviation of residuals and the Akaike's Information Criteria. The result reveals that the Exponential Curve Factor model was the best model that described the experimental data well. Moreover, there was not a direct or indirect relation between the kinetic coefficients of the AD process with the varying total or volatile solid content. (author)

  17. Anaerobic Digestion of Buffalo Dung: Simulation of Process Kinetics

    Directory of Open Access Journals (Sweden)

    Abdul Razaque Sahito

    2015-01-01

    Full Text Available Assessment of kinetic of AD (Anaerobic Digestion is a beneficial practice to forecast the performance of the process. It is helpful in the design of AD vessels, substrate feeding and digestate exit systems. The aim of this work was to assess the kinetics of anaerobically digested buffalo dung at different quantities of water added. It comprises the assessment of the specific methane production on the basis of VS (Volatile Solids added in each reactor by using three first order models, i.e. the modified Gompertz model, the Cone model and the Exponential Curve Factor model. The analysis was tested by using the three statistical parameters, i.e. the coefficient of multiple determinations, the standard deviation of residuals and the Akaike?s Information Criteria. The result reveals that the Exponential Curve Factor model was the best model that described the experimental data well. Moreover, there was not a direct or indirect relation between the kinetic coefficients of the AD process with the varying total or volatile solid content

  18. 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.

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

    DEFF Research Database (Denmark)

    Dederichs, Anne

    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....

  20. Effects of chemical kinetics and starting material regeneration on the efficiency of an iodine laser amplifier

    International Nuclear Information System (INIS)

    A model of the chemical kinetics occurring in an iodine laser amplifier is presented and used to calculate the degree to which the starting material is consumed as a result of laser operation. The cost of purchasing new starting material is estimated and shown to be prohibitive. A scheme for regenerating the starting material from the species present in the amplifier after lasing is proposed. It is shown that the estimated efficiency of this chemical regeneration process is appreciably higher than the projected optimum efficiency of the pumping process

  1. Effects of chemical kinetics and starting material regeneration on the efficiency of an iodine laser amplifier

    Energy Technology Data Exchange (ETDEWEB)

    Fisk, G.A.

    1977-05-01

    A model of the chemical kinetics occurring in an iodine laser amplifier is presented and used to calculate the degree to which the starting material is consumed as a result of laser operation. The cost of purchasing new starting material is estimated and shown to be prohibitive. A scheme for regenerating the starting material from the species present in the amplifier after lasing is proposed. It is shown that the estimated efficiency of this chemical regeneration process is appreciably higher than the projected optimum efficiency of the pumping process.

  2. Molecular dynamics simulation of a chemical reaction

    International Nuclear Information System (INIS)

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

  3. Homogenizing a Nickel-Based Superalloy: Thermodynamic and Kinetic Simulation and Experimental Results

    Energy Technology Data Exchange (ETDEWEB)

    Paul D. Jablonski; Christopher J. Cowen

    2009-03-01

    If the chemical inhomogeneity profile is known a priori, kinetic modeling software such as diffusion-controlled transformations (DICTRA) can be used to model the homogenization kinetics of an alloy. In this study, the Scheil module within the Thermo-Calc software was used to predict the as-cast segregation present within the Ni-based superalloy Nimonic 105. The segregation profiles were read into DICTRA to refine the homogenization heat treatment of this alloy. The thermodynamic and kinetic modeling of the computationally predicted heat treatment and microstructure, and subsequent experimental verification on a real casting of Nimonic 105, are presented.

  4. Protein folding kinetics and thermodynamics from atomistic simulation

    DEFF Research Database (Denmark)

    Piana, Stefano; Lindorff-Larsen, Kresten; Shaw, David E.

    2012-01-01

    Advances in simulation techniques and computing hardware have created a substantial overlap between the timescales accessible to atomic-level simulations and those on which the fastest-folding proteins fold. Here we demonstrate, using simulations of four variants of the human villin headpiece, how......¦-values, and folding pathways provides support for the notion that a norleucine double mutant of villin folds five times faster than the wild-type sequence, but following a slightly different pathway. This work showcases how computer simulation has now developed into a mature tool for the quantitative computational...

  5. On Validity of Linear Phenomenological Nonequilibrium Thermodynamics Equations in Chemical Kinetics

    International Nuclear Information System (INIS)

    The chemical equilibrium state is treated as a fundamental ''reference frame'' in description of chemical reaction. In a definition of reactive absolute activities for components in chemical reaction the difference of chemical potential and its value in the equilibrium is used. The chemical reaction rate is shown to be proportional to the force Xnew defined as the difference of reactive absolute activities of reactants and products. The force Xnew is shown to be equivalent to the force following from chemical kinetics equations and compared with the reduced affinity X as well as with the force of Ross and Mazur XRM = 1 - exp(-X). The force Xnew coincides with X and XRM near to the chemical equilibrium state. A range of the molar fraction of product, in which a difference between the forces Xnew and X is relatively small, is larger than it would be for the forces XRM and X. It means that for some chemical reactions the formalism of linear nonequilibrium thermodynamics can be used in wider ranges than usually expected. Particular analysis is presented for simple reactions. (author)

  6. Process/Equipment Co-Simulation on Syngas Chemical Looping Process

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Liang; Zhou, Qiang; Fan, Liang-Shih

    2012-09-30

    The chemical looping strategy for fossil energy applications promises to achieve an efficient energy conversion system for electricity, liquid fuels, hydrogen and/or chemicals generation, while economically separate CO{sub 2} by looping reaction design in the process. Chemical looping particle performance, looping reactor engineering, and process design and applications are the key drivers to the success of chemical looping process development. In order to better understand and further scale up the chemical looping process, issues such as cost, time, measurement, safety, and other uncertainties need to be examined. To address these uncertainties, advanced reaction/reactor modeling and process simulation are highly desired and the modeling efforts can accelerate the chemical looping technology development, reduce the pilot-scale facility design time and operating campaigns, as well as reduce the cost and technical risks. The purpose of this work is thus to conduct multiscale modeling and simulations on the key aspects of chemical looping technology, including particle reaction kinetics, reactor design and operation, and process synthesis and optimization.

  7. Multiscale Simulations: From Enzyme Kinetics to Fluctuating Hydrodynamics

    OpenAIRE

    Shang, Barry Zhongqi

    2013-01-01

    The development of multiscale methods for computational simulation of biophysical systems represents a significant challenge. Effective computational models that bridge physical insights obtained from atomistic simulations and experimental findings are lacking. An accurate passing of information between these scales would enable: (1) an improved physical understanding of structure-function relationships, and (2) enhanced rational strategies for molecular engineering and materials design. Two ...

  8. Exploring Simulator Use in the Preparation of Chemical Engineers

    Science.gov (United States)

    Yerrick, Randy; Lund, Carl; Lee, Yonghee

    2013-01-01

    In this manuscript, we report the impact of students' usage of a simulator in the preparation of chemical engineers. This case study was conducted using content pretest and posttests, survey questionnaires, interviews, classroom observations, and an analysis of students' written response to design problems. Results showed the use of simulator was…

  9. Comparison between kinetic and fluid simulations of slab ion temperature gradient driven turbulence

    International Nuclear Information System (INIS)

    A detailed comparison between kinetic and fluid simulations of collisionless slab ion temperature gradient (ITG) driven turbulence is made. The nondissipative closure model (NCM) for linearly unstable modes, which is presented by Sugama, Watanabe, and Horton [Phys. Plasmas 8, 2617 (2001)], and the dissipative closure model by Hammett and Perkins (HP) [Phys. Rev. Lett. 64, 3019 (1990)] are used in separate fluid simulations. The validity of these closure models for quantitative prediction of the turbulent thermal transport is examined by comparing nonlinear results of the fluid simulations with those of the collisionless kinetic simulation of high accuracy. Simulation results show that, in the saturated turbulent state, the turbulent thermal diffusivity χ obtained from the HP model is significantly larger than the χ given by the NCM which is closer to χ measured in the kinetic simulation. Contrary to the dissipative form of the parallel heat flux closure relation assumed in the HP model, the NCM describes well the exact kinetic simulation, in which for some unstable wave numbers k, the imaginary part of the ratio of the parallel heat flux qk to the temperature fluctuation Tk is a oscillatory function of time and sometimes takes positive values. The positive values of Im(qk/Tk), imply the negative parallel heat diffusivity, correlate with the occasional inward heat flux occurring for the wave numbers k, and reduce the total χ. (author)

  10. Simulation of chemical reaction dynamics on an NMR quantum computer

    OpenAIRE

    Lu, Dawei; Xu, Nanyang; Xu, Ruixue; Chen, Hongwei; Gong, Jiangbin; Peng, Xinhua; Du, Jiangfeng

    2011-01-01

    Quantum simulation can beat current classical computers with minimally a few tens of qubits and will likely become the first practical use of a quantum computer. One promising application of quantum simulation is to attack challenging quantum chemistry problems. Here we report an experimental demonstration that a small nuclear-magnetic-resonance (NMR) quantum computer is already able to simulate the dynamics of a prototype chemical reaction. The experimental results agree well with classical ...

  11. Using cheminformatics to find simulants for chemical warfare agents

    International Nuclear Information System (INIS)

    Highlights: → Summary of chemical warfare agent (CWA) simulants in current use. → Application of method of molecular similarity to CWA and simulants. → Quantitative metric for CWA-simulant similarity. → Rank ordering of simulants in current use. → Potential of method to identify simulants for emerging agents. - Abstract: Direct experimentation with chemical warfare agents (CWA) to study important problems such as their permeation across protective barrier materials, decontamination of equipment and facilities, or the environmental transport and fate of CWAs is not feasible because of the obvious toxicity of the CWAs and associated restrictions on their laboratory use. The common practice is to use 'simulants,' namely, analogous chemicals that closely resemble the CWAs but are less toxic, with the expectation that the results attained for simulants can be correlated to how the CWAs would perform. Simulants have been traditionally chosen by experts, by means of intuition, using similarity in one or more physical properties (such as vapor pressure or aqueous solubility) or in the molecular structural features (such as functional groups) between the stimulant and the CWA. This work is designed to automate the simulant identification process backed by quantitative metrics, by means of chemical similarity search software routinely used in pharmaceutical drug discovery. The question addressed here is: By the metrics of such software, how similar are traditional simulants to CWAs? That is, what is the numerical 'distance' between each CWA and its customary simulants in the quantitative space of molecular descriptors? The answers show promise for finding close but less toxic simulants for the ever-increasing numbers of CWAs objectively and fast.

  12. Cellulose pyrolysis kinetics in a simulated solar environment

    Energy Technology Data Exchange (ETDEWEB)

    Tobatabaie-Raissi, A. (Florida Solar Energy Center, Cape Canaveral, FL (USA)); Mok, W.S.- L; Antal, M.J., Jr. (Hawaii Univ., Honolulu, HI (USA). Dept. of Mechanical Engineering)

    1989-06-01

    The instrumentation and methods required to study rapid, radiative decomposition of highly reactive biopolymers are described and used to determine the kinetic parameters for the pyrolysis of Avicel PH105 microcrystalline cellulose. Experiments were carried out at heating rates greater than 2K/s in a specially fabricated thermogravimetric analyzer system which employed a 30-kW{sub e}/2-kW/th downward-facing beam, arc-image furnace as a heat source. The thermogravimetric data were interpreted assuming a simple, single-step reaction mechanism and using a nonlinear least-squares kinetic analysis. Based on the results, and apparent activation energy of 100.5 {plus minus} 3kJ/mol, a preexonential factor of in (A (s{sup 1})) = 14 {plus minus} 0.5, and nearly a first-order (n = 0.9 {plus minus} 0.05) reaction were obtained. The extent of char formation was determined experimentally and found to be in the range 6.6-8.4% by weight of original dry material depending upon the prevailing reaction conditions.

  13. Nanocrystallization kinetics under instantaneous growth approximation: Experiments and cellular automata simulations

    Energy Technology Data Exchange (ETDEWEB)

    Blazquez, J.S.; Millan, M.; Conde, C.F.; Conde, A. [Departamento de Fisica de la Materia Condensada, Universidad de Sevilla-ICMSE, P.O. Box 1065, 41080 Sevilla (Spain)

    2010-05-15

    Nanocrystallization kinetics is analyzed in the frame of instantaneous growth approximation, which implies that the time required for a crystallite to reach its final size is negligible with respect to the time required for the nanocrystallization process. This approach strongly simplifies the kinetic analysis and allows us to obtain the nucleation rate from both isothermal and non-isothermal nanocrystallization processes. Moreover, as no constraining mechanism is considered but the absence of growth, the results could be discussed in the frame of Johnson-Mehl-Avrami-Kolmogorov theory with a growth index equal to zero. Cellular automata simulations are in agreement with the observed kinetics and microstructure. (Abstract Copyright [2010], Wiley Periodicals, Inc.)

  14. Dislocation dynamics simulations with climb: kinetics of dislocation loop coarsening controlled by bulk diffusion

    International Nuclear Information System (INIS)

    Dislocation climb mobilities, assuming vacancy bulk diffusion, are derived and implemented in dislocation dynamics simulations to study the coarsening of vacancy prismatic loops in fcc metals. When loops cannot glide, comparison of the simulations with a coarsening model based on the line tension approximation shows good agreement. Dislocation dynamics simulations with both glide and climb are then performed. Allowing for glide of the loops along their prismatic cylinders leads to faster coarsening kinetics, as direct coalescence of the loops is now possible. (authors)

  15. 5D Tempest simulations of kinetic edge turbulence

    Science.gov (United States)

    Xu, X. Q.; Xiong, Z.; Cohen, B. I.; Cohen, R. H.; Dorr, M. R.; Hittinger, J. A.; Kerbel, G. D.; Nevins, W. M.; Rognlien, T. D.; Umansky, M. V.; Qin, H.

    2006-10-01

    Results are presented from the development and application of TEMPEST, a nonlinear five dimensional (3d2v) gyrokinetic continuum code. The simulation results and theoretical analysis include studies of H-mode edge plasma neoclassical transport and turbulence in real divertor geometry and its relationship to plasma flow generation with zero external momentum input, including the important orbit-squeezing effect due to the large electric field flow-shear in the edge. In order to extend the code to 5D, we have formulated a set of fully nonlinear electrostatic gyrokinetic equations and a fully nonlinear gyrokinetic Poisson's equation which is valid for both neoclassical and turbulence simulations. Our 5D gyrokinetic code is built on 4D version of Tempest neoclassical code with extension to a fifth dimension in binormal direction. The code is able to simulate either a full torus or a toroidal segment. Progress on performing 5D turbulence simulations will be reported.

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

    Science.gov (United States)

    Li, Tiejun; Lin, Feng

    2016-04-01

    Motivated by the study of rare events for a typical genetic switching model in systems biology, in this paper we aim to establish the general two-scale large deviations for chemical reaction systems. We build a formal approach to explicitly obtain the large deviation rate functionals for the considered two-scale processes based upon the second quantization path integral technique. We get three important types of large deviation results when the underlying two timescales are in three different regimes. This is realized by singular perturbation analysis to the rate functionals obtained by the path integral. We find that the three regimes possess the same deterministic mean-field limit but completely different chemical Langevin approximations. The obtained results are natural extensions of the classical large volume limit for chemical reactions. We also discuss its implication on the single-molecule Michaelis-Menten kinetics. Our framework and results can be applied to understand general multi-scale systems including diffusion processes.

  17. Advances in petascale kinetic plasma simulation with VPIC and Roadrunner

    Energy Technology Data Exchange (ETDEWEB)

    Bowers, Kevin J [Los Alamos National Laboratory; Albright, Brian J [Los Alamos National Laboratory; Yin, Lin [Los Alamos National Laboratory; Daughton, William S [Los Alamos National Laboratory; Roytershteyn, Vadim [Los Alamos National Laboratory; Kwan, Thomas J T [Los Alamos National Laboratory

    2009-01-01

    VPIC, a first-principles 3d electromagnetic charge-conserving relativistic kinetic particle-in-cell (PIC) code, was recently adapted to run on Los Alamos's Roadrunner, the first supercomputer to break a petaflop (10{sup 15} floating point operations per second) in the TOP500 supercomputer performance rankings. They give a brief overview of the modeling capabilities and optimization techniques used in VPIC and the computational characteristics of petascale supercomputers like Roadrunner. They then discuss three applications enabled by VPIC's unprecedented performance on Roadrunner: modeling laser plasma interaction in upcoming inertial confinement fusion experiments at the National Ignition Facility (NIF), modeling short pulse laser GeV ion acceleration and modeling reconnection in magnetic confinement fusion experiments.

  18. Intermittency in flux driven kinetic simulations of trapped ion turbulence

    International Nuclear Information System (INIS)

    Flux driven kinetic transport is analysed for deeply trapped ion turbulence with the code GYSELA. The main observation is the existence of a steady state situation with respect to the statistics, in particular the balance between the injected energy and the time averaged energy flowing out through the outer edge boundary layer. The temperature is characterised by a very bursty behaviour with a skewed PDF. Superimposed to these short time scale fluctuations, one finds a regime with a strong increase of the zonal flows and a quenching of the turbulent energy. During this phase of such a predator-prey cycle, the core temperature rapidly increases while the edge temperature gradually decreases. The end of this reduced transport regime is governed by the onset of turbulence that governs large relaxation events, and a strong modification of the zonal flow pattern. (authors)

  19. 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.

  20. SLUDGE BATCH 6/TANK 40 SIMULANT CHEMICAL PROCESS CELL SIMULATIONS

    Energy Technology Data Exchange (ETDEWEB)

    Koopman, David

    2010-04-28

    Phase III simulant flowsheet testing was completed using the latest composition estimates for SB6/Tank 40 feed to DWPF. The goals of the testing were to determine reasonable operating conditions and assumptions for the startup of SB6 processing in the DWPF. Testing covered the region from 102-159% of the current DWPF stoichiometric acid equation. Nitrite ion concentration was reduced to 90 mg/kg in the SRAT product of the lowest acid run. The 159% acid run reached 60% of the DWPF Sludge Receipt and Adjustment Tank (SRAT) limit of 0.65 lb H2/hr, and then sporadically exceeded the DWPF Slurry Mix Evaporator (SME) limit of 0.223 lb H2/hr. Hydrogen generation rates peaked at 112% of the SME limit, but higher than targeted wt% total solids levels may have been partially responsible for rates seen. A stoichiometric factor of 120% met both objectives. A processing window for SB6 exists from 102% to something close to 159% based on the simulant results. An initial recommendation for SB6 processing is at 115-120% of the current DWPF stoichiometric acid equation. The addition of simulated Actinide Removal Process (ARP) and Modular Caustic Side Solvent Extraction Unit (MCU) streams to the SRAT cycle had no apparent impact on the preferred stoichiometric factor. Hydrogen generation occurred continuously after acid addition in three of the four tests. The three runs at 120%, 118.4% with ARP/MCU, and 159% stoichiometry were all still producing around 0.1 lb hydrogen/hr at DWPF scale after 36 hours of boiling in the SRAT. The 120% acid run reached 23% of the SRAT limit and 37% of the SME limit. Conversely, nitrous oxide generation was subdued compared to previous sludge batches, staying below 29 lb/hr in all four tests or about a fourth as much as in comparable SB4 testing. Two processing issues, identified during SB6 Phase II flowsheet testing and qualification simulant testing, were monitored during Phase III. Mercury material balance closure was impacted by acid stoichiometry

  1. Chemical kinetics and relaxation of non-equilibrium air plasma generated by energetic photon and electron beams

    Science.gov (United States)

    Maulois, Melissa; Ribière, Maxime; Eichwald, Olivier; Yousfi, Mohammed; Azaïs, Bruno

    2016-04-01

    The comprehension of electromagnetic perturbations of electronic devices, due to air plasma-induced electromagnetic field, requires a thorough study on air plasma. In the aim to understand the phenomena at the origin of the formation of non-equilibrium air plasma, we simulate, using a volume average chemical kinetics model (0D model), the time evolution of a non-equilibrium air plasma generated by an energetic X-ray flash. The simulation is undertaken in synthetic air (80% N2 and 20% O2) at ambient temperature and atmospheric pressure. When the X-ray flash crosses the gas, non-relativistic Compton electrons (low energy) and a relativistic Compton electron beam (high energy) are simultaneously generated and interact with the gas. The considered chemical kinetics scheme involves 26 influent species (electrons, positive ions, negative ions, and neutral atoms and molecules in their ground or metastable excited states) reacting following 164 selected reactions. The kinetics model describing the plasma chemistry was coupled to the conservation equation of the electron mean energy, in order to calculate at each time step of the non-equilibrium plasma evolution, the coefficients of reactions involving electrons while the energy of the heavy species (positive and negative ions and neutral atoms and molecules) is assumed remaining close to ambient temperature. It has been shown that it is the relativistic Compton electron beam directly created by the X-ray flash which is mainly responsible for the non-equilibrium plasma formation. Indeed, the low energy electrons (i.e., the non-relativistic ones) directly ejected from molecules by Compton collisions contribute to less than 1% on the creation of electrons in the plasma. In our simulation conditions, a non-equilibrium plasma with a low electron mean energy close to 1 eV and a concentration of charged species close to 1013 cm-3 is formed a few nanoseconds after the peak of X-ray flash intensity. 200 ns after the flash

  2. CHEMICAL REACTIONS SIMULATED BY GROUND-WATER-QUALITY MODELS.

    Science.gov (United States)

    Grove, David B.; Stollenwerk, Kenneth G.

    1987-01-01

    Recent literature concerning the modeling of chemical reactions during transport in ground water is examined with emphasis on sorption reactions. The theory of transport and reactions in porous media has been well documented. Numerous equations have been developed from this theory, to provide both continuous and sequential or multistep models, with the water phase considered for both mobile and immobile phases. Chemical reactions can be either equilibrium or non-equilibrium, and can be quantified in linear or non-linear mathematical forms. Non-equilibrium reactions can be separated into kinetic and diffusional rate-limiting mechanisms. Solutions to the equations are available by either analytical expressions or numerical techniques. Saturated and unsaturated batch, column, and field studies are discussed with one-dimensional, laboratory-column experiments predominating. A summary table is presented that references the various kinds of models studied and their applications in predicting chemical concentrations in ground waters.

  3. 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

  4. Nonlinear kinetic modeling and simulations of Raman scattering in a two-dimensional geometry

    Directory of Open Access Journals (Sweden)

    Bénisti Didier

    2013-11-01

    Full Text Available In this paper, we present our nonlinear kinetic modeling of stimulated Raman scattering (SRS by the means of envelope equations, whose coefficients have been derived using a mixture of perturbative and adiabatic calculations. First examples of the numerical resolution of these envelope equations in a two-dimensional homogeneous plasma are given, and the results are compared against those of particle-in-cell (PIC simulations. These preliminary comparisons are encouraging since our envelope code provides threshold intensities consistent with those of PIC simulations while requiring computational resources reduced by 4 to 5 orders of magnitude compared to full-kinetic codes.

  5. Simulation studies of plasma waves in the electron foreshock - The transition from reactive to kinetic instability

    Science.gov (United States)

    Dum, C. T.

    1990-06-01

    Particle simulation experiments were used to analyze the electron beam-plasma instability. It is shown that there is a transition from the reactive state of the electron beam-plasma instability to the kinetic instability of Langmuir waves. Quantitative tests, which include an evaluation of the dispersion relation for the evolving non-Maxwellian beam distribution, show that a quasi-linear theory describes the onset of this transition and applies again fully to the kinetic stage. This stage is practically identical to the late stage seen in simulations of plasma waves in the electron foreshock described by Dum (1990).

  6. 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.

  7. 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.

  8. Challenges in simulation of chemical processes in combustion furnaces

    Energy Technology Data Exchange (ETDEWEB)

    Hupa, M.; Kilpinen, P. [Aabo Akademi, Turku (Finland)

    1996-12-31

    The presentation gives an introduction to some of the present issues and problems in treating the complex chemical processes in combustion. The focus is in the coupling of the hydrocarbon combustion process with nitrogen oxide formation and destruction chemistry in practical furnaces or flames. Detailed kinetic modelling based on schemes of elementary reactions are shown to be a useful novel tool for identifying and studying the key reaction paths for nitrogen oxide formation and destruction in various systems. The great importance of the interaction between turbulent mixing and combustion chemistry is demonstrated by the sensitivity of both methane oxidation chemistry and fuel nitrogen conversion chemistry to the reactor and mixing pattern chosen for the kinetic calculations. The fluidized bed combustion (FBC) nitrogen chemistry involves several important heterogeneous reactions. Particularly the char in the bed plays an essential role. Recent research has advanced rapidly and the presentation proposes an overall picture of the fuel nitrogen reaction routes in circulating FBC conditions. (author)

  9. Thermodynamic and Kinetic Investigation of a Chemical Reaction-Based Miniature Heat Pump

    OpenAIRE

    Flueckiger, Scott M.; Volle, Fabien; Garimella, S V; Mongia, Rajiv K.

    2012-01-01

    Representative reversible endothermic chemical reactions (paraldehyde depolymerization and 2-proponal dehydrogenation) are theoretically assessed for their use in a chemical heat pump design for compact thermal management applications. Equilibrium and dynamic simulations are undertaken to explore the operation of the heat pump which upgrades waste heat from near room temperature by approximately 20 in a minimized system volume. A model is developed based on system mass and energy balances cou...

  10. Molecular Dynamics Simulations of Solutions at Constant Chemical Potential

    CERN Document Server

    Perego, Claudio; Parrinello, Michele

    2015-01-01

    Molecular Dynamics studies of chemical processes in solution are of great value in a wide spectrum of applications, that range from nano-technology to pharmaceutical chemistry. However, these calculations are affected by severe finite-size effects, such as the solution being depleted as the chemical process proceeds, that influence the outcome of the simulations. To overcome these limitations, one must allow the system to exchange molecules with a macroscopic reservoir, thus sampling a Grand-Canonical ensemble. Despite the fact that different remedies have been proposed, this still represents a key challenge in molecular simulations. In the present work we propose the C$\\mu$MD method, which introduces an external force that controls the environment of the chemical process of interest. This external force, drawing molecules from a finite reservoir, maintains the chemical potential constant in the region where the process takes place. We have applied the C$\\mu$MD method to the paradigmatic case of urea crystall...

  11. 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.)

  12. Energy conserving continuum algorithms for kinetic & gyrokinetic simulations of plasmas

    Science.gov (United States)

    Hakim, A.; Hammett, G. W.; Shi, E.; Stoltzfus-Dueck, T.

    2015-11-01

    We present high-order, energy conserving, continuum algorithms for the solution of gyrokinetic equations for use in edge turbulence simulations. The distribution function is evolved with a discontinuous Galerkin scheme, while the fields are evolved with a continuous finite-element method. These algorithms work for a general, possibly non-canonical, Poisson bracket operator and conserve energy exactly. Benchmark simulations with ETG turbulence in 3X/2V are shown, as well as initial applications of the algorithms to turbulence in a simplified SOL geometry. Sheath boundary conditions with recycling and secondary electron emission are implemented, and a Lenard-Bernstein collision operator is included. Extension of these algorithms to full Vlasov-Maxwell equations are presented. It is shown that with a particular choice of numerical fluxes the total (particle+field) energy is conserved. Algorithms are implemented in a flexible and open-source framework, Gkeyll, which also includes fluid models, allowing potential hybrid simulations of various plasma problems. Supported by the Max-Planck/Princeton Center for Plasma Physics, and DOE Contract DE-AC02-09CH11466.

  13. Tempest simulations of kinetic GAM mode and neoclassical turbulence

    Science.gov (United States)

    Xu, X. Q.; Dimits, A. M.

    2007-11-01

    TEMPEST is a nonlinear five dimensional (3d2v) gyrokinetic continuum code for studies of H-mode edge plasma neoclassical transport and turbulence in real divertor geometry. The 4D TEMPEST code correctly produces frequency, collisionless damping of GAM and zonal flow with fully nonlinear Boltzmann electrons in homogeneous plasmas. For large q=4 to 9, the Tempest simulations show that a series of resonance at higher harmonics v||=φGqR0/n with n=4 become effective. The TEMPEST simulation also shows that GAM exists in edge plasma pedestal for steep density and temperature gradients, and an initial GAM relaxes to the standard neoclassical residual with neoclassical transport, rather than Rosenbluth-Hinton residual due to the presence of ion-ion collisions. The enhanced GAM damping explains experimental BES measurements on the edge q scaling of the GAM amplitude. Our 5D gyrokinetic code is built on 4D Tempest neoclassical code with extension to a fifth dimension in toroidal direction and with 3D domain decompositions. Progress on performing 5D neoclassical turbulence simulations will be reported.

  14. A new hybrid kinetic electron model for full-f gyrokinetic simulations

    Science.gov (United States)

    Idomura, Y.

    2016-05-01

    A new hybrid kinetic electron model is developed for electrostatic full-f gyrokinetic simulations of the ion temperature gradient driven trapped electron mode (ITG-TEM) turbulence at the ion scale. In the model, a full kinetic electron model is applied to the full-f gyrokinetic equation, the multi-species linear Fokker-Planck collision operator, and an axisymmetric part of the gyrokinetic Poisson equation, while in a non-axisymmetric part of the gyrokinetic Poisson equation, turbulent fluctuations are determined only by kinetic trapped electrons responses. By using this approach, the so-called ωH mode is avoided with keeping important physics such as the ITG-TEM, the neoclassical transport, the ambipolar condition, and particle trapping and detrapping processes. The model enables full-f gyrokinetic simulations of ITG-TEM turbulence with a reasonable computational cost. Comparisons between flux driven ITG turbulence simulations with kinetic and adiabatic electrons are presented. Although the similar ion temperature gradients with nonlinear upshift from linear critical gradients are sustained in quasi-steady states, parallel flows and radial electric fields are qualitatively different with kinetic electrons.

  15. The efficiency of driving chemical reactions by a physical non-equilibrium is kinetically controlled.

    Science.gov (United States)

    Göppel, Tobias; Palyulin, Vladimir V; Gerland, Ulrich

    2016-07-27

    An out-of-equilibrium physical environment can drive chemical reactions into thermodynamically unfavorable regimes. Under prebiotic conditions such a coupling between physical and chemical non-equilibria may have enabled the spontaneous emergence of primitive evolutionary processes. Here, we study the coupling efficiency within a theoretical model that is inspired by recent laboratory experiments, but focuses on generic effects arising whenever reactant and product molecules have different transport coefficients in a flow-through system. In our model, the physical non-equilibrium is represented by a drift-diffusion process, which is a valid coarse-grained description for the interplay between thermophoresis and convection, as well as for many other molecular transport processes. As a simple chemical reaction, we consider a reversible dimerization process, which is coupled to the transport process by different drift velocities for monomers and dimers. Within this minimal model, the coupling efficiency between the non-equilibrium transport process and the chemical reaction can be analyzed in all parameter regimes. The analysis shows that the efficiency depends strongly on the Damköhler number, a parameter that measures the relative timescales associated with the transport and reaction kinetics. Our model and results will be useful for a better understanding of the conditions for which non-equilibrium environments can provide a significant driving force for chemical reactions in a prebiotic setting. PMID:27147197

  16. Domain-growth kinetics and aspects of pinning: A Monte Carlo simulation study

    DEFF Research Database (Denmark)

    Castán, T.; Lindgård, Per-Anker

    1991-01-01

    By means of Monte Carlo computer simulations we study the domain-growth kinetics after a quench across a first-order line to very low and moderate temperatures in a multidegenerate system with nonconserved order parameter. The model is a continuous spin model relevant for martensitic transformati......By means of Monte Carlo computer simulations we study the domain-growth kinetics after a quench across a first-order line to very low and moderate temperatures in a multidegenerate system with nonconserved order parameter. The model is a continuous spin model relevant for martensitic...... transformations, surface reconstructions, and magnetic transitions. No external impurities are introduced, but the model has a number of intrinsic, annealable pinning mechanisms, which strongly influences the growth kinetics. It allows a study of pinning effects of three kinds: (a) pinning of domain walls by...

  17. Feasibility Study on the Rod Ejection Simulation with Point Kinetics Model

    Energy Technology Data Exchange (ETDEWEB)

    Jang, Chan Su; Sun, Jung Won; Um, Kil Sup [Korea Nuclear Fuel, Daejeon (Korea, Republic of)

    2010-05-15

    For the export of the nuclear fuel, Korea Nuclear Fuel (KNF) is developing the KNF-owned safety analysis method. As a part of this project, the alternative approach of rod ejection simulation compared to the Final Safety Analysis Report (FSAR) is studied. Per the Kori units 3 and 4 FSAR, one-dimensional neutron kinetics model is used for the rod ejection simulation. Generally, RETRAN, which simulates the response of nuclear steam supply system for most of transients with point kinetics model, is not applied to simulate the fast reactivity-induced transient such as the rod ejection. However, KNF attempts to use RETRAN instead of the existing code for the rod ejection transient analysis to establish the Integrated Safety Analysis Methodology (ISAM). The essential process in this work is to review the applicability of RETRAN. In this paper, presented are the results of this feasibility study

  18. Chemical enrichment of galaxy clusters from hydrodynamical simulations

    OpenAIRE

    Tornatore, L.; Borgani, S.; Dolag, K; Matteucci, F

    2007-01-01

    We present cosmological hydrodynamical simulations of galaxy clusters aimed at studying the process of metal enrichment of the intra--cluster medium (ICM). These simulations have been performed by implementing a detailed model of chemical evolution in the Tree-SPH \\gd code. This model allows us to follow the metal release from SNII, SNIa and AGB stars, by properly accounting for the lifetimes of stars of different mass, as well as to change the stellar initial mass function (IMF), the lifetim...

  19. A multilevel iterative field solver for implicit, kinetic, plasma simulation

    International Nuclear Information System (INIS)

    The equation for electrostatic potential which arises from the implicit moment method in plasma simulation is a nonsymmetric elliptic equation. The authors present results using a simple multigrid method as a preconditioner to General Minimum RESidual (GMRES) to iteratively solve this nonsymmetric elliptic equation in two dimensions. It is demonstrated that a simple multigrid method produces an effective preconditioner. It is also demonstrated that under some conditions the required number of linear iterations is independent of grid dimension. Results are presented for both uniform and nonuniform grid problems

  20. 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.

  1. Multinomial tau-leaping method for stochastic kinetic simulations

    Science.gov (United States)

    Pettigrew, Michel F.; Resat, Haluk

    2007-02-01

    We introduce the multinomial tau-leaping (MτL) method for general reaction networks with multichannel reactant dependencies. The MτL method is an extension of the binomial tau-leaping method where efficiency is improved in several ways. First, τ-leaping steps are determined simply and efficiently using a priori information and Poisson distribution-based estimates of expectation values for reaction numbers over a tentative τ-leaping step. Second, networks are partitioned into closed groups of reactions and corresponding reactants in which no group reactant set is found in any other group. Third, product formation is factored into upper-bound estimation of the number of times a particular reaction occurs. Together, these features allow larger time steps where the numbers of reactions occurring simultaneously in a multichannel manner are estimated accurately using a multinomial distribution. Furthermore, we develop a simple procedure that places a specific upper bound on the total reaction number to ensure non-negativity of species populations over a single multiple-reaction step. Using two disparate test case problems involving cellular processes—epidermal growth factor receptor signaling and a lactose operon model—we show that the τ-leaping based methods such as the MτL algorithm can significantly reduce the number of simulation steps thus increasing the numerical efficiency over the exact stochastic simulation algorithm by orders of magnitude.

  2. Quantifying the Sources of Kinetic Frustration in Folding Simulations of Small Proteins

    OpenAIRE

    Savol, Andrej J.; Chennubhotla, Chakra S.

    2014-01-01

    Experiments and atomistic simulations of polypeptides have revealed structural intermediates that promote or inhibit conformational transitions to the native state during folding. We invoke a concept of “kinetic frustration” to quantify the prevalence and impact of these behaviors on folding rates within a large set of atomistic simulation data for 10 fast-folding proteins, where each protein’s conformational space is represented as a Markov state model of conformational transitions. Our grap...

  3. Monte Carlo simulation of hot-carrier phenomena in open quantum devices: A kinetic approach

    OpenAIRE

    Rossi, Fausto; Proietti Zaccaria, Remo; Iotti, Rita Claudia

    2004-01-01

    An alternative simulation strategy for the study of nonequilibrium carrier dynamics in quantum devices with open boundaries is presented. In particular, we propose replacing the usual modeling of open quantum systems based on phenomenological injection/loss rates with a kinetic description of the system-reservoir thermalization process. More specifically, in this simulation scheme the partial carrier thermalization induced by the device spatial boundaries is treated within the standard Monte ...

  4. KMCLib: A general framework for lattice kinetic Monte Carlo (KMC) simulations

    OpenAIRE

    Leetmaa, Mikael; Skorodumova, Natalia V.

    2014-01-01

    KMCLib is a general framework for lattice kinetic Monte Carlo (KMC) simulations. The program can handle simulations of the diffusion and reaction of millions of particles in one, two, or three dimensions, and is designed to be easily extended and customized by the user to allow for the development of complex custom KMC models for specific systems without having to modify the core functionality of the program. Analysis modules and on-the-fly elementary step diffusion rate calculations can be i...

  5. Improved solution methods of point reactor kinetics equations used in simulator of NPP

    International Nuclear Information System (INIS)

    Two improved solution methods of point reactor kinetics equations, reactivity confinement method and comprehensive method are described. The two methods are more accurate and have less computation time than Hermite Interpolating Multinomial method and variable implicit integration method which is adopted in full scope simulators abroad

  6. Comparisons of dense-plasma-focus kinetic simulations with experimental measurements

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, A. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Link, A. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Welch, D. [Voss Scientific, Inc., Albuquerque, NM (United States); Ellsworth, J. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Falabella, S. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Tang, V. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2014-06-01

    Dense-plasma-focus (DPF) Z-pinch devices are sources of copious high-energy electrons and ions, x rays, and neutrons. The mechanisms through which these physically simple devices generate such high-energy beams in a relatively short distance are not fully understood and past optimization efforts of these devices have been largely empirical. Previously we reported on fully kinetic simulations of a DPF and compared them with hybrid and fluid simulations of the same device. Here we present detailed comparisons between fully kinetic simulations and experimental data on a 1.2 kJ DPF with two electrode geometries, including neutron yield and ion beam energy distributions. A more intensive third calculation is presented which examines the effects of a fully detailed pulsed power driver model. We also compare simulated electromagnetic fluctuations with direct measurement of radiofrequency electromagnetic fluctuations in a DPF plasma. These comparisons indicate that the fully kinetic model captures the essential physics of these plasmas with high fidelity, and provide further evidence that anomalous resistivity in the plasma arises due to a kinetic instability near the lower hybrid frequency.

  7. Nonlinear simulation of tearing mode and m=1 kink mode based on kinetic RMHD model

    International Nuclear Information System (INIS)

    In this paper, we investigate dynamics of sawtooth oscillation and neoclassical tearing modes based on kinetic RMHD model, putting an emphasis on interaction with microscopic and transport processes. The simulation results show that the assumption in the conventional theory of neoclassical tearing mode is rather rude. (author)

  8. The Effect of a Computerized Simulation on Middle School Students' Understanding of the Kinetic Molecular Theory

    Science.gov (United States)

    Stern, Luli; Barnea, Nitza; Shauli, Sofia

    2008-01-01

    The objective of this study was to evaluate the effect of a dynamic software simulation on the understanding of the kinetic molecular theory by 7th graders. Students in the control group (n = 62) studied a curricular unit that addressed the differences in arrangement and motion of molecules in the three phases of matter. The experimental group (n…

  9. A Simulation Game for the Study of Enzyme Kinetics and Inhibition.

    Science.gov (United States)

    Chayoth, Reuben; Cohen, Annette

    1996-01-01

    Presents a simulation game that facilitates understanding of the concepts of enzyme kinetics and inhibition. The first part of the game deals with the relationship between enzyme activity and substrate concentration while the second part deals with characterization of competitive and noncompetitive inhibition of enzyme activity. (JRH)

  10. SLUDGE BATCH 6/TANK 51 SIMULANT CHEMICAL PROCESS CELL SIMULATIONS

    Energy Technology Data Exchange (ETDEWEB)

    Koopman, David; Best, David

    2010-04-28

    Qualification simulant testing was completed to determine appropriate processing conditions and assumptions for the Sludge Batch 6 (SB6) Shielded Cells demonstration of the DWPF flowsheet using the qualification sample from Tank 51 for SB6 after SRNL washing. It was found that an acid addition window of 105-139% of the DWPF acid equation (100-133% of the Koopman minimum acid equation) gave acceptable Sludge Receipt and Adjustment Tank (SRAT) and Slurry Mix Evaporator (SME) results for nitrite destruction and hydrogen generation. Hydrogen generation occurred continuously after acid addition in three of the four tests. The three runs at 117%, 133%, and 150% stoichiometry (Koopman) were all still producing around 0.1 lb hydrogen/hr at DWPF scale after 42 hours of boiling in the SRAT. The 150% acid run reached 110% of the DWPF SRAT limit of 0.65 lb H{sub 2}/hr, and the 133% acid run reached 75% of the DWPF SME limit of 0.223 lb H{sub 2}/hr. Conversely, nitrous oxide generation was subdued compared to previous sludge batches, staying below 25 lb/hr in all four tests or about a fourth as much as in comparable SB4 testing. Two other processing issues were noted. First, incomplete mercury suspension impacted mercury stripping from the SRAT slurry. This led to higher SRAT product mercury concentrations than targeted (>0.45 wt% in the total solids). Associated with this issue was a general difficulty in quantifying the mass of mercury in the SRAT vessel as a function of time, especially as acid stoichiometry increased. About ten times more mercury was found after drying the 150% acid SME product to powder than was indicated by the SME product sample results. Significantly more mercury was also found in the 133% acid SME product samples than was found during the SRAT cycle sampling. It appears that mercury is segregating from the bulk slurry in the SRAT vessel, as mercury amalgam deposits for example, and is not being resuspended by the agitators. The second processing issue

  11. Kinetic Simulation of Fractal Aggregation on Liquid Surfaces

    Institute of Scientific and Technical Information of China (English)

    WU Feng-Min; FANG Yun-Zhang; YE Gao-Xiang; WU Zi-Qin

    2005-01-01

    A modified fractal growth model based on the deposition, diffusion, and aggregation (DDA) with cluster rotation is presented to simulate two-dimensional fractal aggregation on liquid surfaces. The mobility (including diffusion and rotation) of clusters is related to its mass, which is given by Dm = D0s-γD and θm = θ0s-γθ, respectively. We concentrate on revealing the details of the influence of deposition flux F, cluster diffusion factor γD and cluster rotation factor γθ on the dynamics of fractal aggregation on liquid surfaces. It is shown that the morphologies of clusters and values of cluster density and fractal dimension depend dramatically on the deposition flux and migration factors of clusters.

  12. 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.

  13. 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.

  14. Stochastic Simulation of Chemical Exchange in Two Dimensional Infrared Spectroscopy

    CERN Document Server

    Sanda, F; Sanda, Frantisek; Mukamel, Shaul

    2006-01-01

    The stochastic Liouville equations are employed to investigate the combined signatures of chemical exchange (two-state-jump) and spectral diffusion (coupling to an overdamped Brownian oscillator) in the coherent response of an anharmonic vibration to three femtosecond infrared pulses. Simulations reproduce the main features recently observed in the OD stretch of phenol in benzene.

  15. 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.

  16. Photodegradation kinetics, products and mechanism of timolol under simulated sunlight

    International Nuclear Information System (INIS)

    Highlights: ► The indirect degradation of timolol is first investigated in fulvic acid solution. ► 3FA* and 1O2 accounted for the degradation of timolol in the aerated FA solutions. ► The presence of halides inhibited the degradation in the order of Cl− − −. ► The role of I− in the degradation was first found to be concentration-dependent. ► The photoproducts of timolol were identified by LC-DAD/ESI-MS/MS analysis. -- Abstract: The photodegradation of β-blocker timolol in fulvic acid (FA) solution was investigated under simulated sunlight. The triplet excited state of FA (3FA*) and singlet oxygen (1O2) were the main reactive species responsible for the degradation of timolol in the aerated FA solutions. Both dissolved oxygen and iodide ions (I−) are the efficient quenchers of 3FA*. The photodegradation was drastically accelerated after removing the dissolved oxygen. The presence of I− inhibited the photosensitized degradation of timolol in the deoxygenated FA solutions, whereas the role of I− in the reaction was concentration-dependent in the aerated solutions. The other halide ions such as chloride (Cl−) and bromide (Br−) exhibited less effect on the photodegradation of timolol in both aerated and deoxygenated solutions. By LC-DAD/ESI-MS/MS analysis, the photoproducts of timolol in both aerated and deoxygenated FA solutions were identified. Electron transfer interaction occurred between 3FA* and amine moiety of timolol, leading to the cleavage of C–O bond in the side chain and oxidation of the hexatomic ring. These findings suggest the photosensitized degradation was a significant pathway for the elimination of timolol in natural waters

  17. Photodegradation kinetics, products and mechanism of timolol under simulated sunlight

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Yong, E-mail: ychen@hust.edu.cn [School of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Liang, Qi; Zhou, Danna [College of Material Science and Chemical Engineering, China University of Geosciences, Wuhan 430074 (China); Wang, Zongping, E-mail: zongpingw@hust.edu.cn [School of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Tao, Tao [School of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074 (China); Zuo, Yuegang [Department of Chemistry and Biochemistry, University of Massachusetts Dartmouth, 285 Old Westport Road, North Dartmouth, MA 02747 (United States)

    2013-05-15

    Highlights: ► The indirect degradation of timolol is first investigated in fulvic acid solution. ► {sup 3}FA{sup *} and {sup 1}O{sub 2} accounted for the degradation of timolol in the aerated FA solutions. ► The presence of halides inhibited the degradation in the order of Cl{sup −} < Br{sup −} < I{sup −}. ► The role of I{sup −} in the degradation was first found to be concentration-dependent. ► The photoproducts of timolol were identified by LC-DAD/ESI-MS/MS analysis. -- Abstract: The photodegradation of β-blocker timolol in fulvic acid (FA) solution was investigated under simulated sunlight. The triplet excited state of FA ({sup 3}FA{sup *}) and singlet oxygen ({sup 1}O{sub 2}) were the main reactive species responsible for the degradation of timolol in the aerated FA solutions. Both dissolved oxygen and iodide ions (I{sup −}) are the efficient quenchers of {sup 3}FA{sup *}. The photodegradation was drastically accelerated after removing the dissolved oxygen. The presence of I{sup −} inhibited the photosensitized degradation of timolol in the deoxygenated FA solutions, whereas the role of I{sup −} in the reaction was concentration-dependent in the aerated solutions. The other halide ions such as chloride (Cl{sup −}) and bromide (Br{sup −}) exhibited less effect on the photodegradation of timolol in both aerated and deoxygenated solutions. By LC-DAD/ESI-MS/MS analysis, the photoproducts of timolol in both aerated and deoxygenated FA solutions were identified. Electron transfer interaction occurred between {sup 3}FA{sup *} and amine moiety of timolol, leading to the cleavage of C–O bond in the side chain and oxidation of the hexatomic ring. These findings suggest the photosensitized degradation was a significant pathway for the elimination of timolol in natural waters.

  18. Nonlinear kinetic description of Raman growth using an envelope code, and comparisons with Vlasov simulations

    Science.gov (United States)

    Bénisti, Didier; Morice, Olivier; Gremillet, Laurent; Siminos, Evangelos; Strozzi, David J.

    2010-10-01

    In this paper, we present our nonlinear kinetic modeling of stimulated Raman scattering in a uniform and collisionless plasma using envelope equations. We recall the derivation of these equations, as well as our theoretical predictions for each of the nonlinear kinetic terms, the precision of which having been carefully checked against Vlasov simulations. We particularly focus here on the numerical resolution of these equations, which requires the additional concept of "self-optimization" that we explain, and we describe the envelope code BRAMA that we used. As an application of our modeling, we present one-dimensional BRAMA simulations of stimulated Raman scattering which predict threshold intensities, as well as time scales for Raman growth above threshold, in very good agreement with those inferred from Vlasov simulations. Finally, we discuss the differences between our modeling and other published ones.

  19. Nonlinear kinetic description of Raman growth using an envelope code, and comparisons with Vlasov simulations

    International Nuclear Information System (INIS)

    In this paper, we present our nonlinear kinetic modeling of stimulated Raman scattering in a uniform and collisionless plasma using envelope equations. We recall the derivation of these equations, as well as our theoretical predictions for each of the nonlinear kinetic terms, the precision of which having been carefully checked against Vlasov simulations. We particularly focus here on the numerical resolution of these equations, which requires the additional concept of ''self-optimization'' that we explain, and we describe the envelope code BRAMA that we used. As an application of our modeling, we present one-dimensional BRAMA simulations of stimulated Raman scattering which predict threshold intensities, as well as time scales for Raman growth above threshold, in very good agreement with those inferred from Vlasov simulations. Finally, we discuss the differences between our modeling and other published ones.

  20. Simulations of 4D edge transport and dynamics using the TEMPEST gyro-kinetic code

    Science.gov (United States)

    Rognlien, T. D.; Cohen, B. I.; Cohen, R. H.; Dorr, M. R.; Hittinger, J. A. F.; Kerbel, G. D.; Nevins, W. M.; Xiong, Z.; Xu, X. Q.

    2006-10-01

    Simulation results are presented for tokamak edge plasmas with a focus on the 4D (2r,2v) option of the TEMPEST continuum gyro-kinetic code. A detailed description of a variety of kinetic simulations is reported, including neoclassical radial transport from Coulomb collisions, electric field generation, dynamic response to perturbations by geodesic acoustic modes, and parallel transport on open magnetic-field lines. Comparison is made between the characteristics of the plasma solutions on closed and open magnetic-field line regions separated by a magnetic separatrix, and simple physical models are used to qualitatively explain the differences observed in mean flow and electric-field generation. The status of extending the simulations to 5D turbulence will be summarized. The code structure used in this ongoing project is also briefly described, together with future plans.

  1. Numerical Simulation on Removal of NO Under Pulse Corona Discharge by Chemical Kinetic Coupled with Computation Fluid Dynamics%脉冲电晕净化NO的化学动力学耦合流体动力学数值模拟

    Institute of Scientific and Technical Information of China (English)

    侯文慧; 张海茹; 范朋慧; 杨蒙; 仲兆平; 杨宏曼

    2011-01-01

    探讨了利用CHEMKIN4.1与FLUENT6.2软件耦合预测脉冲电晕放电条件下NO的净化过程.利用脉冲放电时间平均集合模型,计算出N2/O2在高能电子撞击下的离解速率常数,提出一套NO/O2/N2体系反应机理.结合CHEMKIN的敏感性分析方法对反应机理进行了分析,预测了活性自由基元(N、O)体积分数的变化趋势,获得了NQ在三维等离子反应器内的的体积分数分布.结果表明,耦合计算很好地解决了计算流体力学与复杂反应动力学机制结合的问题,脉冲电晕放电可以有效地脱除NO,O2体积分数的增加和较低反应温度均有利于NO的脱除.%The numerical simulation for the removal of NO under pulse corona discharge using CHEMKJN4.1 coupled with FLUENT6.2 software was discussed. The reaction rate constant of the ionization of N2/O2 by electron-impact dissociation was calculated by the lumped kinetic model of pulse corona discharge, and a kinetic model in the system of NO/O2/N2 under pulse corona discharge was obtained. The kinetic mechanism was analyzed by the sensitivity analysis method in CHEMKIN. The concentrations of free radicals (N, O)were predicted and the three-dimensional concentration distribution of Nox in plasma reactor was also obtained. The results show that coupling calculation can solve the problem of the combination of the computation fluid dynamics (CFD) and the complex kinetic mechanism, that pulse corona discharge can effectively removes nitric oxide, and that O2 fraction and low temperature are helpful for the removal of NO.

  2. Global Simulation of the GAM Oscillation and Damping in a Drift Kinetic Model

    OpenAIRE

    Satake, S

    2006-01-01

    Collisionless damping of the geodesic acoustic mode (GAM) is investigated by a drift kinetic simulation. The main subject of the study is to analyze how the magnetic configuration and the finite-orbit-width(FOW) effect of the ion drift motion affect the collisionless damping of GAM. We utilize the neoclassical transport code ”FORTEC-3D”, which solves the drift kinetic equation based on the delta-f method, to study these issues. In recent analytical study on GAM and zonal flow it is found that...

  3. 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.

  4. Simulation of precipitation in an aluminum scandium alloy using kinetic Monte Carlo and DBSCAN algorithms

    OpenAIRE

    Moura, Alfredo de; Esteves, António

    2013-01-01

    The present paper reports the precipitation process of Al3Sc structures in an aluminum scandium alloy, which has been simulated with a kinetic Monte Carlo (kMC) method. The kMC implementation is based on the vacancy diffusion mechanism. To filter the raw data generated by the kMC simulation, the density-based clustering with noise (DBSCAN) method was employed. kMC and DBSCAN algorithms were implemented in the C language. The undertaken simulations were conducted in the SeARCH cluster at the U...

  5. Three-dimensional off-lattice Monte Carlo kinetics simulations of interstellar grain chemistry and ice structure

    CERN Document Server

    Garrod, Robin T

    2013-01-01

    The first off-lattice Monte Carlo kinetics model of interstellar dust-grain surface chemistry is presented. The positions of all surface particles are determined explicitly, according to the local potential minima resulting from the pair-wise interactions of contiguous atoms and molecules, rather than by a pre-defined lattice structure. The model is capable of simulating chemical kinetics on any arbitrary dust-grain morphology, as determined by the user-defined positions of each individual dust-grain atom. A simple method is devised for the determination of the most likely diffusion pathways and their associated energy barriers for surface species. The model is applied to a small, idealized dust grain, adopting various gas densities and using a small chemical network. Hydrogen and oxygen atoms accrete onto the grain, to produce H2O, H2, O2 and H2O2. The off-lattice method allows the ice structure to evolve freely; ice mantle porosity is found to be dependent on the gas density, which controls the accretion ra...

  6. Numerical analysis of knock during HCCI in a high compression ratio methanol engine based on LES with detailed chemical kinetics

    International Nuclear Information System (INIS)

    Highlights: • Knock during HCCI in a high compression ratio methanol engine was modeled. • A detailed methanol mechanism was used to simulate the knocking combustion. • Compared with the SI engines, the HCCI knocking combustion burnt faster. • The reaction rate of HCO had two obvious peaks, one was positive, and another was negative. • Compared with the SI engines, the values of the reaction rates of CH2O, H2O2, and HO2 were higher, and it had negative peaks. - Abstract: In this study, knock during HCCI (homogeneous charge compression ignition) was studied based on LES (large eddy simulation) with methanol chemical kinetics (84-reaction, 21-species) in a high compression ratio methanol engine. The non-knocking and knocking combustion of SI (spark ignition) and HCCI engines were compared. The results showed that the auto-ignition spots were initially occurred near the combustion chamber wall. The knocking combustion burnt faster during HCCI than SI methanol engine. The HCO reaction rate was different from SI engine, it had two obvious peaks, one was positive peak, and another was negative peak. Compared with the SI methanol engine, in addition to the concentration of HCO, the concentrations of the other intermediate products and species such as CO, OH, CH2O, H2O2, HO2 were increased significantly; the reaction rates of CH2O, H2O2, and HO2 had negative peaks, and whose values were several times higher than SI methanol engine

  7. A decontamination study of simulated chemical and biological agents

    International Nuclear Information System (INIS)

    A comprehensive decontamination scheme of the chemical and biological agents, including airborne agents and surface contaminating agents, is presented. When a chemical and biological attack occurs, it is critical to decontaminate facilities or equipments to an acceptable level in a very short time. The plasma flame presented here may provide a rapid and effective elimination of toxic substances in the interior air in isolated spaces. As an example, a reaction chamber, with the dimensions of a 22 cm diameter and 30 cm length, purifies air with an airflow rate of 5000 l/min contaminated with toluene, the simulated chemical agent, and soot from a diesel engine, the simulated aerosol for biological agents. Although the airborne agents in an isolated space are eliminated to an acceptable level by the plasma flame, the decontamination of the chemical and biological agents cannot be completed without cleaning surfaces of the facilities. A simulated sterilization study of micro-organisms was carried out using the electrolyzed ozone water. The electrolyzed ozone water very effectively kills endospores of Bacillus atrophaeus (ATCC 9372) within 3 min. The electrolyzed ozone water also kills the vegetative micro-organisms, fungi, and virus. The electrolyzed ozone water, after the decontamination process, disintegrates into ordinary water and oxygen without any trace of harmful materials to the environment

  8. Analysis of exergy loss of gasoline surrogate combustion process based on detailed chemical kinetics

    International Nuclear Information System (INIS)

    Highlights: • We explored the exergy loss sources of gasoline engine like combustion process. • The model combined non-equilibrium thermodynamics with detailed chemical kinetics. • We explored effects of initial conditions on exergy loss of combustion process. • Exergy loss decreases 15% of fuel chemical exergy by design of initial conditions. • Correspondingly, the second law efficiency increases from 38.9% to 68.9%. - Abstract: Chemical reaction is the most important source of combustion irreversibility in premixed conditions, but details of the exergy loss mechanisms have not been explored yet. In this study numerical analysis based on non-equilibrium thermodynamics combined with detailed chemical kinetics is conducted to explore the exergy loss mechanism of gasoline engine like combustion process which is simplified as constant volume combustion. The fuel is represented by the common accepted gasoline surrogates which consist of four components: iso-octane (57%), n-heptane (16%), toluene (23%), and 2-pentene (4%). We find that overall exergy loss is mainly composed of three peaks along combustion generated from chemical reactions in three stages, the conversion from large fuel molecules into small molecules (as Stage 1), the H2O2 loop-related reactions (as Stage 2), and the violent oxidation reactions of CO, H, and O (as Stage 3). The effects of individual combustion boundaries, including temperature, pressure, equivalence ratio, oxygen concentration, on combustion exergy loss have been widely investigated. The combined effects of combustion boundaries on the total loss of gasoline surrogates are also investigated. We find that in a gasoline engine with a compression ratio of 10, the total loss can be reduced from 31.3% to 24.3% using lean combustion. The total loss can be further reduced to 22.4% by introducing exhaust gas recirculation and boosting the inlet charge. If the compression ratio is increased to 17, the total loss can be decreased to 20

  9. Simulation of horizontal slug-flow pneumatic conveying with kinetic theory

    Institute of Scientific and Technical Information of China (English)

    GU Zhengmeng; GUO Liejin

    2007-01-01

    Wavelike slug-flow is a representative flow type in horizontal pneumatic conveying.Kinetic theory was introduced to establish a 3D kinetic numerical model for wavelike slug gas-solid flow in this paper.Wavelike motion of particulate slugs in horizontal pipes was numerically investigated.The formation and motion process of slugs and settled layer were simulated.The characteristics of the flow,such as pressure drop,air velocity distribution,slug length and settled layer thickness,and the detailed changing characteristics of slug length and settled layer thickness with air velocity were obtained.The results indicate that kinetic theory can represent the physical characteristics of the non-suspension dense phase flow of wavelike slug pneumatic conveying.The experiment in this paper introduced a new idea for the numerical calculation of slug-flow pneumatic conveying.

  10. 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)

  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. Determination of Reference Chemical Potential Using Molecular Dynamics Simulations

    Directory of Open Access Journals (Sweden)

    Krishnadeo Jatkar

    2010-01-01

    Full Text Available A new method implementing molecular dynamics (MD simulations for calculating the reference properties of simple gas hydrates has been proposed. The guest molecules affect interaction between adjacent water molecules distorting the hydrate lattice, which requires diverse values of reference properties for different gas hydrates. We performed simulations to validate the experimental data for determining Δ0, the chemical potential difference between water and theoretical empty cavity at the reference state, for structure II type gas hydrates. Simulations have also been used to observe the variation of the hydrate unit cell volume with temperature. All simulations were performed using TIP4P water molecules at the reference temperature and pressure conditions. The values were close to the experimental values obtained by the Lee-Holder model, considering lattice distortion.

  13. SDG-based Model Validation in Chemical Process Simulation

    Institute of Scientific and Technical Information of China (English)

    张贝克; 许欣; 马昕; 吴重光

    2013-01-01

    Signed direct graph (SDG) theory provides algorithms and methods that can be applied directly to chemical process modeling and analysis to validate simulation models, and is a basis for the development of a soft-ware environment that can automate the validation activity. This paper is concentrated on the pretreatment of the model validation. We use the validation scenarios and standard sequences generated by well-established SDG model to validate the trends fitted from the simulation model. The results are helpful to find potential problems, as-sess possible bugs in the simulation model and solve the problem effectively. A case study on a simulation model of boiler is presented to demonstrate the effectiveness of this method.

  14. Benchmark test of drift-kinetic and gyrokinetic codes through neoclassical transport simulations

    International Nuclear Information System (INIS)

    Two simulation codes that solve the drift-kinetic or gyrokinetic equation in toroidal plasmas are benchmarked by comparing the simulation results of neoclassical transport. The two codes are the drift-kinetic δf Monte Carlo code (FORTEC-3D) and the gyrokinetic full- f Vlasov code (GT5D), both of which solve radially-global, five-dimensional kinetic equation with including the linear Fokker-Planck collision operator. In a tokamak configuration, neoclassical radial heat flux and the force balance relation, which relates the parallel mean flow with radial electric field and temperature gradient, are compared between these two codes, and their results are also compared with the local neoclassical transport theory. It is found that the simulation results of the two codes coincide very well in a wide rage of plasma collisionality parameter ν* = 0.01 - 10 and also agree with the theoretical estimations. The time evolution of radial electric field and particle flux, and the radial profile of the geodesic acoustic mode frequency also coincide very well. These facts guarantee the capability of GT5D to simulate plasma turbulence transport with including proper neoclassical effects of collisional diffusion and equilibrium radial electric field. (author)

  15. Comparing kinetic and fluid simulations of scrape-off layer physics

    Science.gov (United States)

    Churchill, R. M.; Canik, J. M.; Chang, C. S.; Hager, R.; Leonard, A. W.; Maingi, R.; Nazikian, R.; Stotler, D. P.

    2015-11-01

    Simulations using the fully kinetic code XGCa were undertaken to explore the impact of kinetic effects on scrape-off layer (SOL) physics in DIII-D H-mode plasmas. XGCa is a total-f, gyrokinetic code which self-consistently calculates the axisymmetric electrostatic potential and plasma dynamics, and includes modules for neutral Monte Carlo transport. Fluid simulations are usually used to simulate the SOL, due to its high collisionality. However, a number of discrepancies have been observed between experiment and leading SOL fluid codes (e.g. SOLPS), including underestimating outer target temperatures, radial electric field in the SOL, parallel ion SOL flows at the low field side, and impurity radiation. Many of these discrepancies may be linked to the fluid treatment, and could be resolved by including kinetic effects in SOL simulations. Status of benchmarking efforts to compare XGCa with the fluid code SOLPS and traditional two-point models will be presented in the sheath-limited and medium-recycling regimes, including future plans to compare results in the high-recycling and detached regimes. This work supported by U.S. DoE contracts DE- AC02-09CH11466 and DE-FG02-06ER5484.

  16. ASPEN: A fully kinetic, reduced-description particle-in-cell model for simulating parametric instabilities

    International Nuclear Information System (INIS)

    A fully kinetic, reduced-description particle-in-cell (RPIC) model is presented in which deviations from quasineutrality, electron and ion kinetic effects, and nonlinear interactions between low-frequency and high-frequency parametric instabilities are modeled correctly. The model is based on a reduced description where the electromagnetic field is represented by three separate temporal envelopes in order to model parametric instabilities with low-frequency and high-frequency daughter waves. Because temporal envelope approximations are invoked, the simulation can be performed on the electron time scale instead of the time scale of the light waves. The electrons and ions are represented by discrete finite-size particles, permitting electron and ion kinetic effects to be modeled properly. The Poisson equation is utilized to ensure that space-charge effects are included. The RPIC model is fully three dimensional and has been implemented in two dimensions on the Accelerated Strategic Computing Initiative (ASCI) parallel computer at Los Alamos National Laboratory, and the resulting simulation code has been named ASPEN. The authors believe this code is the first particle-in-cell code capable of simulating the interaction between low-frequency and high-frequency parametric instabilities in multiple dimensions. Test simulations of stimulated Raman scattering, stimulated Brillouin scattering, and Langmuir decay instability are presented

  17. Kinetic electron and ion instability of the lunar wake simulated at physical mass ratio

    Energy Technology Data Exchange (ETDEWEB)

    Haakonsen, Christian Bernt, E-mail: chaako@mit.edu; Hutchinson, Ian H., E-mail: ihutch@mit.edu; Zhou, Chuteng, E-mail: ctzhou@mit.edu [Plasma Science and Fusion Center, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States)

    2015-03-15

    The solar wind wake behind the moon is studied with 1D electrostatic particle-in-cell (PIC) simulations using a physical ion to electron mass ratio (unlike prior investigations); the simulations also apply more generally to supersonic flow of dense magnetized plasma past non-magnetic objects. A hybrid electrostatic Boltzmann electron treatment is first used to investigate the ion stability in the absence of kinetic electron effects, showing that the ions are two-stream unstable for downstream wake distances (in lunar radii) greater than about three times the solar wind Mach number. Simulations with PIC electrons are then used to show that kinetic electron effects can lead to disruption of the ion beams at least three times closer to the moon than in the hybrid simulations. This disruption occurs as the result of a novel wake phenomenon: the non-linear growth of electron holes spawned from a narrow dimple in the electron velocity distribution. Most of the holes arising from the dimple are small and quickly leave the wake, approximately following the unperturbed electron phase-space trajectories, but some holes originating near the center of the wake remain and grow large enough to trigger disruption of the ion beams. Non-linear kinetic-electron effects are therefore essential to a comprehensive understanding of the 1D electrostatic stability of such wakes, and possible observational signatures in ARTEMIS data from the lunar wake are discussed.

  18. 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

  19. 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.

  20. 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...

  1. Experimental study of methane hydrate formation kinetics with or without additives and modeling based on chemical affinity

    International Nuclear Information System (INIS)

    Highlights: • Applying chemical affinity for investigating the effects of additives. • Effects of thermodynamic additives on methane hydrate formation kinetics. • Determining kinetic parameters for methane hydrate formation with additives. • A unique path for the methane hydrate formation with aqueous solution of addetives. - Abstract: In this work, methane hydrate formation process (as a process for energy conversion and cool-energy storage) with or without additives was investigated. First, the effects of initial pressure and three surfactants (sodium dodecyl sulfate (SDS), dodecyltrimethyl ammonium bromide (DTAB) and Triton X-100 (TX-100)) and two thermodynamic additives (tetrahydrofuran (THF) and tetra butyl ammonium bromide (TBAB)) on methane hydrate formation kinetics were experimentally studied. Then the macroscopic modeling of methane hydrate formation kinetics with and without additives based on chemical affinity was done. The kinetic parameters of the chemical affinity model were determined for methane hydrate formation with and without additives. The effects of initial pressure and additives on the chemical affinity model parameters were also investigated. In addition, the results of the model were in a good agreement with experimental data

  2. XCHEM-1D: A Heat Transfer/Chemical Kinetics Computer Program for multilayered reactive materials

    Energy Technology Data Exchange (ETDEWEB)

    Gross, R.J.; Baer, M.R.; Hobbs, M.L.

    1993-10-01

    An eXplosive CHEMical kinetics code, XCHEM, has been developed to solve the reactive diffusion equations associated with thermal ignition of energetic materials. This method-of-lines code uses stiff numerical methods and adaptive meshing to resolve relevant combustion physics. Solution accuracy is maintained between multilayered materials consisting of blends of reactive components and/or inert materials. Phase change and variable properties are included in one-dimensional slab, cylindrical and spherical geometries. Temperature-dependent thermal properties have been incorporated and the modification of thermal conductivities to include decomposition effects are estimated using solid/gas volume fractions determined by species fractions. Gas transport properties, including high pressure corrections, have also been included. Time varying temperature, heat flux, convective and thermal radiation boundary conditions, and layer to layer contact resistances have also been implemented.

  3. 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.

  4. 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.

  5. Analysis of two phase mass transfer kinetics by logarithmic driving force based on chemical thermodynamics

    International Nuclear Information System (INIS)

    Interphase transfer kinetics of neodymium and nitric acid was studied using a single drop column with recycling organic phase via an external mixing vessel in H2O-HNO3/NaNO3-Nd(NO3)3-tri-n-butylphosphate system. Experimental data have been analyzed by two new concepts for driving forces for transport: synthesized linear and logarithmic forms. The former is defined as geometrical-mean driving force, and the latter is the logarithm of the product of reciprocals of concentration ratios x/xe and y/ye against equilibrium states in each phase, i.e. ln{xe·ye)/(x·y)}. By applying thermodynamic logarithmic form of driving force along reaction coordinate, the net transfer fluxes of neodymium and nitric acid have been represented by chemical affinity under high ionic strengths over a wide range of solvent loading as flux=flux degf(1-exp(-A/RT)). (author)

  6. 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.

  7. Simulations of turbulence and dispersion in idealized urban canopies using a new kinetic scheme

    Science.gov (United States)

    Wang, Lian-Ping; Huq, Pablo; Guo, Zhaoli

    2015-11-01

    In this talk, we will demonstrate the capabilities of a new kinetic scheme, known as the Discrete Unified Gas Kinetic Scheme (DUGKS), by simulating turbulent flow and scalar dispersion in an idealized urban canopy. DUGKS is a finite-volume formulation of the Boltzmann equation which can incorporate a non-uniform grid. It could be used as an direct numerical simulation tool or as a large-eddy simulation tool for turbulent flow in a complex geometry. We will describe this mesoscopic CFD method, and details in setting up a non-uniform grid, no-slip boundary condition on solid surfaces, and far-field boundary conditions. The model urban canopy contains an array of buildings with a prescribed building-height-to-width aspect ratio. Several aspect ratios will be considered in the simulations. A passive scalar is continuously released from a near-ground point source. Profiles of mean velocity, turbulence statistics, and scalar concentration obtained from the simulations will be compared to data from water-tunnel measurements. Grid refinement will be performed to study the convergence of the simulated results on the grid resolution.

  8. Annealing kinetics of single displacement cascades in Ni: An atomic scale computer simulation

    International Nuclear Information System (INIS)

    In order to describe the long term evolution of the defects produced by a displacement cascade, Molecular dynamics (MD) and Kinetic Monte Carlo (KMC) methods are employed. Using an empirical Ni interatomic potential in MD, the damage resulting from primary knock-on atom (PKA) energies up to 30 keV has been simulated. The annealing kinetics and the fraction of freely migrating defects (FMD) are determined for each single displacement cascade, by a KMC code which is based on a set of parameters extracted mainly from MD simulations. It allows an atomistic study of the evolution of the initial damage over a time scale up to 100s and the determination of the fraction of the defects that escape the KMC box, compared to those obtained by MD, as function of temperature and PKA energy. It has been found that this fraction depends strongly on the temperature but reaches a saturation value above stage V

  9. A hydrodynamics-reaction kinetics coupled model for evaluating bioreactors derived from CFD simulation.

    Science.gov (United States)

    Wang, Xu; Ding, Jie; Guo, Wan-Qian; Ren, Nan-Qi

    2010-12-01

    Investigating how a bioreactor functions is a necessary precursor for successful reactor design and operation. Traditional methods used to investigate flow-field cannot meet this challenge accurately and economically. Hydrodynamics model can solve this problem, but to understand a bioreactor in sufficient depth, it is often insufficient. In this paper, a coupled hydrodynamics-reaction kinetics model was formulated from computational fluid dynamics (CFD) code to simulate a gas-liquid-solid three-phase biotreatment system for the first time. The hydrodynamics model is used to formulate prediction of the flow field and the reaction kinetics model then portrays the reaction conversion process. The coupled model is verified and used to simulate the behavior of an expanded granular sludge bed (EGSB) reactor for biohydrogen production. The flow patterns were visualized and analyzed. The coupled model also demonstrates a qualitative relationship between hydrodynamics and biohydrogen production. The advantages and limitations of applying this coupled model are discussed. PMID:20727741

  10. Numerical simulation of rising bubble with chemical reaction

    Science.gov (United States)

    Sahu, Kirti; Tripathi, Manoj; Matar, Omar; Karapetsas, George

    2014-11-01

    The dynamics of a rising bubble under the action of gravity and in the presence of an exothermic chemical reaction at the interface is investigated via direct numerical simulation using Volume-of-Fluid (VOF) method. The product of the chemical reaction, and temperature rise due to the exothermic chemical reaction influence the local viscosity and surface tension near the interfacial region, which in turn give rise to many interesting dynamics. The flow is governed by continuity, Navier-Stokes equations along with the convection equation of the volume fraction of the outer fluid and the energy equation. The effects of the Bond, Damkohler, and Reynolds numbers, and of the dimensionless heat of reaction are investigated. The results of this parametric study will be presented at the meeting.

  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. Stochastic method for accommodation of equilibrating basins in kinetic Monte Carlo simulations

    OpenAIRE

    Van Siclen, Clinton DeW.

    2008-01-01

    A computationally simple way to accommodate 'basins' of trapping sites in standard kinetic Monte Carlo simulations is presented. By assuming the system is effectively equilibrated in the basin, the residence time (time spent in the basin before escape) and the probabilities for transition to states outside the basin may be calculated. This is demonstrated for point defect diffusion over a periodic grid of sites containing a complex basin.

  13. Kinetic simulations of X-B and O-X-B mode conversion

    Energy Technology Data Exchange (ETDEWEB)

    Arefiev, A. V., E-mail: alexey@austin.utexas.edu [Institute for Fusion Studies, The University of Texas, Austin, Texas 78712 (United States); Du Toit, E. J.; Vann, R. G. L. [York Plasma Institute, Department of Physics, University of York, York (United Kingdom); Köhn, A. [IGVP, University of Stuttgart, Stuttgart (Germany); Max Planck Institute for Plasma Physics, Garching (Germany); Holzhauer, E. [IGVP, University of Stuttgart, Stuttgart (Germany); Shevchenko, V. F. [EURATOM/CCFE Fusion Association, Culham Science Centre, Abingdon (United Kingdom)

    2015-12-10

    We have performed fully-kinetic simulations of X-B and O-X-B mode conversion in one and two dimensional setups using the PIC code EPOCH. We have recovered the linear dispersion relation for electron Bernstein waves by employing relatively low amplitude incoming waves. The setups presented here can be used to study non-linear regimes of X-B and O-X-B mode conversion.

  14. Mass Accommodation of Water: Bridging the Gap Between Molecular Dynamics Simulations and Kinetic Condensation Models

    OpenAIRE

    Julin, Jan; Shiraiwa, Manabu; Miles, Rachael E H; Reid, Jonathan P.; Pöschl, Ulrich; Riipinen, Ilona

    2013-01-01

    The condensational growth of submicrometer aerosol particles to climate relevant sizes is sensitive to their ability to accommodate vapor molecules, which is described by the mass accommodation coefficient. However, the underlying processes are not yet fully understood. We have simulated the mass accommodation and evaporation processes of water using molecular dynamics, and the results are compared to the condensation equations derived from the kinetic gas theory to shed light on the compatib...

  15. Coarse-grained kinetic scheme-based simulation framework for solution growth of ZnO nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Alvi, Farah, E-mail: falvi@mail.usf.edu [University of South Florida, Department of Electrical Engineering (United States); Joshi, Rakesh K. [University of South Florida, Department of Mechanical Engineering (United States); Huang, Qiang [University of Southern California, Daniel J. Epstein Department of Industrial and Systems Engineering (United States); Kumar, Ashok [University of South Florida, Department of Mechanical Engineering (United States)

    2011-06-15

    Kinetic Monte Carlo (KMC)-based stochastic model is used to understand the growth of zinc oxide nanowires from aqueous solution containing chemical precursors and capping agent. Through a hydrothermal growth mechanism, the average diameter of zinc oxide wires obtained is around 300 nm, whereas the length is order of several micrometers. Our Monte Carlo algorithm is based on the continuous-time Monte Carlo algorithm of Bortz, Kalos and Lebowitz (BKL) methodology. Both reactions and diffusion mechanisms assigning stochastic probabilities have been simulated. In algorithm, the ZnO atoms were treated as individual particles which diffuse in solution substrate and interact with other type of atoms. Once attached with growing nanowires, the diffusion rate of ZnO atom is considerably reduced. Since in a KMC algorithm each atom can be represented individually therefore, internal noise is automatically incorporated.

  16. 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

    intermediate temperature combustion pathways of 25DMF. Hydroxyl radical addition to the furan ring is highlighted as an important fuel consuming reaction, leading to the formation of methyl vinyl ketone and acetyl radical. The chemically activated recombination of HȮ2 or CH3Ȯ2 with the 5-methyl-2-furanylmethyl radical, forming a 5-methyl-2-furylmethanoxy radical and ȮH or CH3Ȯ radical is also found to exhibit significant control over ignition delay times, as well as being important reactions in the prediction of species profiles in a JSR. Kinetics for the abstraction of a hydrogen atom from the alkyl side-chain of the fuel by molecular oxygen and HȮ2 radical are found to be sensitive in the estimation of ignition delay times for fuel-air mixtures from temperatures of 820-1200 K. At intermediate temperatures, the resonantly stabilised 5-methyl-2-furanylmethyl radical is found to predominantly undergo bimolecular reactions, and as a result sub-mechanisms for 5-methyl-2-formylfuran and 5-methyl-2-ethylfuran, and their derivatives, have also been developed with consumption pathways proposed. This study is the first to attempt to simulate the combustion of these species in any detail, although future refinements are likely necessary. The current study illustrates both quantitatively and qualitatively the complex chemical behavior of what is a high potential biofuel. Whilst the current work is the most comprehensive study on the oxidation of 25DMF in the literature to date, the mechanism cannot accurately reproduce laminar burning velocity measurements over a suitable range of unburnt gas temperatures, pressures and equivalence ratios, although discrepancies in the experimental literature data are highlighted. Resolving this issue should remain a focus of future work. PMID:24273333

  17. 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.

  18. 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)

  19. Kinetics of microbial degradation of deicing chemicals in percolated porous media - the modeling perspective

    Science.gov (United States)

    Wehrer, Markus; Lissner, Heidi; Totsche, Kai

    2013-04-01

    A quantitative knowledge of the fate of deicing chemicals in the subsurface can be provided by analysis of laboratory and field experiments with numerical simulation models. In the present study, experimental data of microbial degradation of the deicing chemical propylene glycol (PG) under flow conditions in soil columns and field lysimeters were simulated to analyze the process conditions of degradation and to obtain the according parameters. Results from the column experiment were evaluated applying different scenarios of an advection-dispersion model using HYDRUS-1D. To reconstruct the data, different competing degradation models were included, i.e., zero order, first order and inclusion of a growing and decaying biomass. The general breakthrough behavior of propylene glycol in soil columns can be simulated well using a coupled model of solute transport and degradation with growth and decay of biomass. The susceptibility of the model to non-unique solutions was investigated using systematical forward and inverse simulations. We found that the model tends to equifinal solutions under certain conditions. Complex experimental boundary conditions can help to avoid this. Under field conditions, the situation is far more complex than in the laboratory. Studying the fate of PG with undisturbed lysimeters we found that aerobic and anaerobic degradation occurs simultaneously. We attribute this to the physical structure and the aggregated nature of the undisturbed soil material . This results in the presence of spatially disjoint oxidative and reductive regions of microbial activity and requires, but is not fully reflected by a dual porosity model. Currently, the numerical simulation of this system is in progress, considering several flow and transport models. A stochastic global search algorithm (DREAM-ZS) is used in conjuction with HYDRUS-1D to avoid local minima in the inverse simulations. The study shows the current limitations and potentials of modeling degradation

  20. Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP: linking condensation, evaporation and chemical reactions of organics, oxidants and water

    Directory of Open Access Journals (Sweden)

    M. Shiraiwa

    2011-12-01

    Full Text Available We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KM-GAP that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KM-GAP is based on the PRA model framework (Pöschl-Rudich-Ammann, 2007, and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modeled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmospheric aerosols and clouds.

    In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at ~270 K is close to unity. Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for efficient probing of specific physical effects and parameters. With regard to oxidative aging of organic aerosol particles, we illustrate how the

  1. Parallelization of kinetic Monte Carlo algorithm to simulate AL3Sc precipitation

    OpenAIRE

    Moura, Alfredo de; Esteves, António

    2015-01-01

    The present paper reports the precipitation process of Al3Sc structures in an aluminum scandium alloy, which has been simulated with a synchronous parallel kinetic Monte Carlo (spkMC) algorithm. The spkMC implementation is based on the vacancy diffusion mechanism. To filter the raw data generated by the spkMC simulations, the density-based clustering with noise (DBSCAN) method has been employed. spkMC and DBSCAN algorithms were implemented in the C language and using MPI library. The simulati...

  2. On grain growth kinetics in two-phase polycrystalline materials through Monte Carlo simulation

    Indian Academy of Sciences (India)

    K R Phaneesh; Anirudh Bhat; Gautam Mukherjee; K T Kashyap

    2013-08-01

    Monte Carlo Potts model simulation was carried out on a 2D square lattice for various surface fractions of second phase particles for over 50,000 iterations. The observations are in good agreement with known theoretical and experimental results with respect to both growth kinetics as well as grain size distribution. Further, the average grain size and the largest grain size were computed for various surface fractions which have indicated normal grain growth and microstructure homogeneity. The surface fraction of the second phase particles interacting with the grain boundaries (), hitherto not computed through the simulation route, is shown to vary inversely as the average grain size due to Zener pinning.

  3. Kinetic Monte Carlo simulation of formation of microstructures in liquid droplets

    Energy Technology Data Exchange (ETDEWEB)

    Block, M [Institut fuer Theoretische Physik, Technische Universitaet Berlin, D-10623 Berlin (Germany); Kunert, R [Institut fuer Theoretische Physik, Technische Universitaet Berlin, D-10623 Berlin (Germany); Schoell, E [Institut fuer Theoretische Physik, Technische Universitaet Berlin, D-10623 Berlin (Germany); Boeck, T [Institut fuer Kristallzuechtung Berlin, D-12489 Berlin (Germany); Teubner, Th [Institut fuer Kristallzuechtung Berlin, D-12489 Berlin (Germany)

    2004-11-01

    We study the deposition of indium droplets on a glass surface and the subsequent formation of silicon microcrystals inside these droplets. Kinetic Monte Carlo methods are used to analyse the influence of growth temperature, flux of incoming particles, surface coverage, and in particular an energy parameter simulating the surface tension, upon the morphology of growth. According to the experimental conditions of crystallization, a temperature gradient and diffusion in spherical droplets are included. The simulations explain the formation of silicon crystal structures in good agreement with the experiment. The dependence of their shape and the conditions of formation on the growth parameters are investigated in detail.

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

    Science.gov (United States)

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

    2015-07-01

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

  5. 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.

  6. Evaluating gyro-viscosity in the Kelvin-Helmholtz instability by kinetic simulations

    Science.gov (United States)

    Umeda, Takayuki; Yamauchi, Natsuki; Wada, Yasutaka; Ueno, Satoshi

    2016-05-01

    In the present paper, the finite-Larmor-radius (gyro-viscous) term [K. V. Roberts and J. B. Taylor, Phys. Rev. Lett. 8, 197-198 (1962)] is evaluated by using a full kinetic Vlasov simulation result of the Kelvin-Helmholtz instability (KHI). The velocity field and the pressure tensor are calculated from the high-resolution data of the velocity distribution functions obtained by the Vlasov simulation, which are used to approximate the Finite-Larmor-Radius (FLR) term according to Roberts and Taylor [Phys. Rev. Lett. 8, 197-198 (1962)]. The direct comparison between the pressure tensor and the FLR term shows an agreement. It is also shown that the anisotropic pressure gradient enhanced the linear growth of the KHI when the inner product between the vorticity of the primary velocity shear layer and the magnetic field is negative, which is consistent with the previous FLR-magnetohydrodynamic simulation result. This result suggests that it is not sufficient for reproducing the kinetic simulation result by fluid simulations to include the FLR term (or the pressure tensor) only in the equation of motion for fluid.

  7. Kinetic lattice Monte-Carlo simulations on the ordering kinetics of free and supported FePt L10-nanoparticles

    OpenAIRE

    Michael Müller; Karsten Albe

    2011-01-01

    The ordering kinetics in free and supported L10 nanoparticles was studied by means of lattice-based kinetic Monte-Carlo simulations. Starting from a fully disordered particle of Wulff shape, the simulations show that the nucleation of ordered domains is starting quickly on various (100) facets but is retarded in the particle volume due to the lack of vacancies compared with a thin film geometry. If a substrate is present, we do not find significant differences in the ordering behavior. This h...

  8. Kinetic simulation of the electron-cyclotron maser instability: effect of a finite source size

    CERN Document Server

    Kuznetsov, A A

    2012-01-01

    The electron-cyclotron maser instability is widespread in the Universe, producing, e.g., radio emission of the magnetized planets and cool substellar objects. Diagnosing the parameters of astrophysical radio sources requires comprehensive nonlinear simulations of the radiation process. We simulate the electron-cyclotron maser instability in a very low-beta plasma. The model used takes into account the radiation escape from the source region and the particle flow through this region. We developed a kinetic code to simulate the time evolution of an electron distribution in a radio emission source. The model includes the terms describing the particle injection to and escape from the emission source region. The spatial escape of the emission from the source is taken into account by using a finite amplification time. The unstable electron distribution of the horseshoe type is considered. A number of simulations were performed for different parameter sets typical of the magnetospheres of planets and ultracool dwarf...

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-02-08

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

  10. 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…

  11. 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

  12. 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…

  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. 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.

  15. 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

  16. 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

  17. Comparison of different moment-closure approximations for stochastic chemical kinetics

    International Nuclear Information System (INIS)

    In recent years, moment-closure approximations (MAs) of the chemical master equation have become a popular method for the study of stochastic effects in chemical reaction systems. Several different MA methods have been proposed and applied in the literature, but it remains unclear how they perform with respect to each other. In this paper, we study the normal, Poisson, log-normal, and central-moment-neglect MAs by applying them to understand the stochastic properties of chemical systems whose deterministic rate equations show the properties of bistability, ultrasensitivity, and oscillatory behaviour. Our results suggest that the normal MA is favourable over the other studied MAs. In particular, we found that (i) the size of the region of parameter space where a closure gives physically meaningful results, e.g., positive mean and variance, is considerably larger for the normal closure than for the other three closures, (ii) the accuracy of the predictions of the four closures (relative to simulations using the stochastic simulation algorithm) is comparable in those regions of parameter space where all closures give physically meaningful results, and (iii) the Poisson and log-normal MAs are not uniquely defined for systems involving conservation laws in molecule numbers. We also describe the new software package MOCA which enables the automated numerical analysis of various MA methods in a graphical user interface and which was used to perform the comparative analysis presented in this paper. MOCA allows the user to develop novel closure methods and can treat polynomial, non-polynomial, as well as time-dependent propensity functions, thus being applicable to virtually any chemical reaction system

  18. Comparison of different moment-closure approximations for stochastic chemical kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Schnoerr, David [School of Biological Sciences, University of Edinburgh, Edinburgh (United Kingdom); School of Informatics, University of Edinburgh, Edinburgh (United Kingdom); Sanguinetti, Guido [School of Informatics, University of Edinburgh, Edinburgh (United Kingdom); Grima, Ramon [School of Biological Sciences, University of Edinburgh, Edinburgh (United Kingdom)

    2015-11-14

    In recent years, moment-closure approximations (MAs) of the chemical master equation have become a popular method for the study of stochastic effects in chemical reaction systems. Several different MA methods have been proposed and applied in the literature, but it remains unclear how they perform with respect to each other. In this paper, we study the normal, Poisson, log-normal, and central-moment-neglect MAs by applying them to understand the stochastic properties of chemical systems whose deterministic rate equations show the properties of bistability, ultrasensitivity, and oscillatory behaviour. Our results suggest that the normal MA is favourable over the other studied MAs. In particular, we found that (i) the size of the region of parameter space where a closure gives physically meaningful results, e.g., positive mean and variance, is considerably larger for the normal closure than for the other three closures, (ii) the accuracy of the predictions of the four closures (relative to simulations using the stochastic simulation algorithm) is comparable in those regions of parameter space where all closures give physically meaningful results, and (iii) the Poisson and log-normal MAs are not uniquely defined for systems involving conservation laws in molecule numbers. We also describe the new software package MOCA which enables the automated numerical analysis of various MA methods in a graphical user interface and which was used to perform the comparative analysis presented in this paper. MOCA allows the user to develop novel closure methods and can treat polynomial, non-polynomial, as well as time-dependent propensity functions, thus being applicable to virtually any chemical reaction system.

  19. Comparison of different moment-closure approximations for stochastic chemical kinetics

    Science.gov (United States)

    Schnoerr, David; Sanguinetti, Guido; Grima, Ramon

    2015-11-01

    In recent years, moment-closure approximations (MAs) of the chemical master equation have become a popular method for the study of stochastic effects in chemical reaction systems. Several different MA methods have been proposed and applied in the literature, but it remains unclear how they perform with respect to each other. In this paper, we study the normal, Poisson, log-normal, and central-moment-neglect MAs by applying them to understand the stochastic properties of chemical systems whose deterministic rate equations show the properties of bistability, ultrasensitivity, and oscillatory behaviour. Our results suggest that the normal MA is favourable over the other studied MAs. In particular, we found that (i) the size of the region of parameter space where a closure gives physically meaningful results, e.g., positive mean and variance, is considerably larger for the normal closure than for the other three closures, (ii) the accuracy of the predictions of the four closures (relative to simulations using the stochastic simulation algorithm) is comparable in those regions of parameter space where all closures give physically meaningful results, and (iii) the Poisson and log-normal MAs are not uniquely defined for systems involving conservation laws in molecule numbers. We also describe the new software package MOCA which enables the automated numerical analysis of various MA methods in a graphical user interface and which was used to perform the comparative analysis presented in this paper. MOCA allows the user to develop novel closure methods and can treat polynomial, non-polynomial, as well as time-dependent propensity functions, thus being applicable to virtually any chemical reaction system.

  20. Integration of the 3D kinetics code QUABOX/CUBBOX in the GRS analysis simulator-ATLAS based on ATHLET

    International Nuclear Information System (INIS)

    The paper describes the successfully performed verification tests with the ATLAS simulator environment and the coupled QUABOX/CUBBOX-ATHLET code system with enhanced option of switching from point kinetics (PK) to 3D calculations. (authors)

  1. Gyrokinetic and kinetic particle-in-cell simulations of guide-field reconnection

    Science.gov (United States)

    Munoz Sepulveda, Patricio Alejandro; Büchner, Jörg; Kilian, Patrick; Told, Daniel; Jenko, Frank

    2016-07-01

    Fully kinetic Particle-in-Cell (PIC) simulations of (strong) guide-field reconnection can be computationally very demanding, due to the intrinsic stability and accuracy conditions required by this numerical method. One convenient approach to circumvent this issue is using gyrokinetic theory, an approximation of the Vlasov-Maxwell equations for strongly magnetized plasmas that eliminates the fast gyromotion, and thus reduces the computational cost. Although previous works have started to compare the features of reconnection between both approaches, a complete understanding of the differences is far from being complete. This knowledge is essential to discern the limitations of the gyrokinetic simulations of magnetic reconnection when applied to scenarios with moderate guide fields, such as the Solar corona, in contrast to most of the fusion/laboratory plasmas. We extend a previous work by our group, focused in the differences in the macroscopic flows, by analyzing the heating processes and non-thermal features developed by reconnection between both plasma approximations. We relate these processes by identifying some high-frequency cross-streaming instabilities appearing only in the fully kinetic approach. We characterize the effects of these phenonema such as anisotropic electron heating, beam formation and turbulence under different parameter regimes. And finally, we identify the conditions under which these instabilities tends to become negligible in the fully kinetic model, and thus a comparison with gyrokinetic theory becomes more reliable.

  2. Multi-scale modelling and numerical simulation of electronic kinetic transport

    International Nuclear Information System (INIS)

    This research thesis which is at the interface between numerical analysis, plasma physics and applied mathematics, deals with the kinetic modelling and numerical simulations of the electron energy transport and deposition in laser-produced plasmas, having in view the processes of fuel assembly to temperature and density conditions necessary to ignite fusion reactions. After a brief review of the processes at play in the collisional kinetic theory of plasmas, with a focus on basic models and methods to implement, couple and validate them, the author focuses on the collective aspect related to the free-streaming electron transport equation in the non-relativistic limit as well as in the relativistic regime. He discusses the numerical development and analysis of the scheme for the Vlasov-Maxwell system, and the selection of a validation procedure and numerical tests. Then, he investigates more specific aspects of the collective transport: the multi-specie transport, submitted to phase-space discontinuities. Dealing with the multi-scale physics of electron transport with collision source terms, he validates the accuracy of a fast Monte Carlo multi-grid solver for the Fokker-Planck-Landau electron-electron collision operator. He reports realistic simulations for the kinetic electron transport in the frame of the shock ignition scheme, the development and validation of a reduced electron transport angular model. He finally explores the relative importance of the processes involving electron-electron collisions at high energy by means a multi-scale reduced model with relativistic Boltzmann terms

  3. HIDENEK: an implicit particle simulation of kinetic-MHD phenomena in three-dimensional plasmas

    International Nuclear Information System (INIS)

    An advanced 'kinetic-MHD' simulation method and its applications to plasma physics are given in this lecture. This method is quite suitable for studying strong nonlinear, kinetic processes associated with large space-scale, low-frequency electromagnetic phenomena of plasmas. A full set of the Maxwell equations, and the Newton-Lorentz equations of motion for particle ions and guiding-center electrons are adopted. In order to retain only the low-frequency waves and instabilities, implicit particle-field equations are derived. The present implicit-particle method is proved to reproduce the MHD eigenmodes such as Alfven, magnetosonic and kinetic Alfven waves in a thermally near-equilibrium plasma. In the second part of the lecture, several physics applications are shown. These include not only the growth of the instabilities of beam ions against the background plasmas and helical kink of the current, but they also demonstrate nonlinear results such as pitch-angle scattering of the ions. Recent progress in the simulation of the Kelvin-Helmholtz instability is also presented with a special emphasis on the mixing of plasma particles. (author)

  4. Kinetic Electron and Ion Instability of the Lunar Wake Simulated at Physical Mass Ratio

    CERN Document Server

    Haakonsen, Christian Bernt; Zhou, Chuteng

    2015-01-01

    The solar wind wake behind the moon is studied with 1D electrostatic particle-in-cell (PIC) simulations using a physical ion to electron mass ratio (unlike prior investigations); the simulations also apply more generally to supersonic flow of dense magnetized plasma past non-magnetic objects. A hybrid electrostatic Boltzmann electron treatment is first used to investigate the ion stability in the absence of kinetic electron effects, showing that the ions are two-stream unstable for downstream wake distances (in lunar radii) greater than about three times the solar wind Mach number. Simulations with PIC electrons are then used to show that kinetic electron effects can lead to disruption of the ion streams at least three times closer to the moon than in the hybrid simulations. This disruption occurs as the result of a novel wake phenomenon: the non-linear growth of electron holes spawned from a narrow dimple in the electron velocity distribution. Most of the holes arising from the dimple are small and quickly l...

  5. Understanding filamentary growth in electrochemical metallization memory cells using kinetic Monte Carlo simulations

    Science.gov (United States)

    Menzel, Stephan; Kaupmann, Philip; Waser, Rainer

    2015-07-01

    We report on a 2D kinetic Monte Carlo model that describes the resistive switching in electrochemical metallization cells. To simulate the switching process, we consider several different processes on the atomic scale: electron-transfer reactions at the boundaries, ion migration, adsorption/desorption from/to interfaces, surface diffusion and nucleation. These processes result in a growth/dissolution of a metallic filament within an insulating matrix. In addition, the model includes electron tunneling between the growing filament and the counter electrode, which allows for simulating multilevel switching. It is shown that the simulation model can reproduce the reported switching kinetics, switching variability and multilevel capabilities of ECM devices. As a major result, the influence of mechanical stress working on the host matrix due to the filamentary growth is investigated. It is demonstrated that the size and shape of the filament depend on the Young's modulus of the insulating matrix. For high values a wire-like structure evolves, whereas the shape is dendritic if the Young's modulus is negligible.We report on a 2D kinetic Monte Carlo model that describes the resistive switching in electrochemical metallization cells. To simulate the switching process, we consider several different processes on the atomic scale: electron-transfer reactions at the boundaries, ion migration, adsorption/desorption from/to interfaces, surface diffusion and nucleation. These processes result in a growth/dissolution of a metallic filament within an insulating matrix. In addition, the model includes electron tunneling between the growing filament and the counter electrode, which allows for simulating multilevel switching. It is shown that the simulation model can reproduce the reported switching kinetics, switching variability and multilevel capabilities of ECM devices. As a major result, the influence of mechanical stress working on the host matrix due to the filamentary growth is

  6. Mass accommodation of water: bridging the gap between molecular dynamics simulations and kinetic condensation models.

    Science.gov (United States)

    Julin, Jan; Shiraiwa, Manabu; Miles, Rachael E H; Reid, Jonathan P; Pöschl, Ulrich; Riipinen, Ilona

    2013-01-17

    The condensational growth of submicrometer aerosol particles to climate relevant sizes is sensitive to their ability to accommodate vapor molecules, which is described by the mass accommodation coefficient. However, the underlying processes are not yet fully understood. We have simulated the mass accommodation and evaporation processes of water using molecular dynamics, and the results are compared to the condensation equations derived from the kinetic gas theory to shed light on the compatibility of the two. Molecular dynamics simulations were performed for a planar TIP4P-Ew water surface at four temperatures in the range 268-300 K as well as two droplets, with radii of 1.92 and 4.14 nm at T = 273.15 K. The evaporation flux from molecular dynamics was found to be in good qualitative agreement with that predicted by the simple kinetic condensation equations. Water droplet growth was also modeled with the kinetic multilayer model KM-GAP of Shiraiwa et al. [Atmos. Chem. Phys. 2012, 12, 2777]. It was found that, due to the fast transport across the interface, the growth of a pure water droplet is controlled by gas phase diffusion. These facts indicate that the simple kinetic treatment is sufficient in describing pure water condensation and evaporation. The droplet size was found to have minimal effect on the value of the mass accommodation coefficient. The mass accommodation coefficient was found to be unity (within 0.004) for all studied surfaces, which is in agreement with previous simulation work. Additionally, the simulated evaporation fluxes imply that the evaporation coefficient is also unity. Comparing the evaporation rates of the mass accommodation and evaporation simulations indicated that the high collision flux, corresponding to high supersaturation, present in typical molecular dynamics mass accommodation simulations can under certain conditions lead to an increase in the evaporation rate. Consequently, in such situations the mass accommodation coefficient

  7. 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

  8. Chemical Simulations of Prebiotic Molecules: Interstellar Ethanimine Isomers

    Science.gov (United States)

    Quan, Donghui; Herbst, Eric; Corby, Joanna F.; Durr, Allison; Hassel, George

    2016-06-01

    The E- and Z-isomers of ethanimine (CH3CHNH) were recently detected toward the star-forming region Sagittarius (Sgr) B2(N) using the Green Bank Telescope PRIMOS cm-wave spectral data, and imaged by the Australia Telescope Compact Array. Ethanimine is not reported in the hot cores of Sgr B2, but only in gas that absorbs at +64 and +82 km s‑1 in the foreground of continuum emission generated by H ii regions. The ethanimine isomers can serve as precursors of the amino acid alanine and may play important roles in forming biological molecules in the interstellar medium. Here we present a study of the chemistry of ethanimine using a gas-grain simulation based on rate equations, with both isothermal and warm-up conditions. In addition, the density, kinetic temperature, and cosmic ray ionization rate have been varied. For a variety of physical conditions in the warm-up models for Sgr B2(N) and environs, the simulations show reasonable agreement with observationally obtained abundances. Isothermal models of translucent clouds along the same line of sight yield much lower abundances, so that ethanimine would be much more difficult to detect in these sources despite the fact that other complex molecules have been detected there.

  9. Kinetics of Hexagonal Cylinders to Face-centered Cubic Spheres Transition of Triblock Copolymer in Selective Solvent: Brownian Dynamics Simulation

    OpenAIRE

    LI Minghai; Liu, Yongsheng; Bansil, Rama

    2010-01-01

    The kinetics of the transformation from the hexagonal packed cylinder (HEX) phase to the face-centered-cubic (FCC) phase was simulated using Brownian Dynamics for an ABA triblock copolymer in a selective solvent for the A block. The kinetics was obtained by instantaneously changing either the temperature of the system or the well-depth of the Lennard-Jones potential. Detailed analysis showed that the transformation occurred via a rippling mechanism. The simulation results indicated that the o...

  10. 3-D kinetics simulations of the NRU reactor using the DONJON code

    International Nuclear Information System (INIS)

    The NRU reactor is highly heterogeneous, heavy-water cooled and moderated, with online refuelling capability. It is licensed to operate at a maximum power of 135 MW, with a peak thermal flux of approximately 4.0 x 1018 n.m-2 . s-1. In support of the safe operation of NRU, three-dimensional kinetics calculations for reactor transients have been performed using the DONJON code. The code was initially designed to perform space-time kinetics calculations for the CANDUR power reactors. This paper describes how the DONJON code can be applied to perform neutronic simulations for the analysis of reactor transients in NRU, and presents calculation results for some transients. (authors)

  11. A hybrid model for coupling kinetic corrections of fusion reactivity to hydrodynamic implosion simulations

    Science.gov (United States)

    Tang, Xian-Zhu; McDevitt, C. J.; Guo, Zehua; Berk, H. L.

    2014-03-01

    Inertial confinement fusion requires an imploded target in which a central hot spot is surrounded by a cold and dense pusher. The hot spot/pusher interface can take complicated shape in three dimensions due to hydrodynamic mix. It is also a transition region where the Knudsen and inverse Knudsen layer effect can significantly modify the fusion reactivity in comparison with the commonly used value evaluated with background Maxwellians. Here, we describe a hybrid model that couples the kinetic correction of fusion reactivity to global hydrodynamic implosion simulations. The key ingredient is a non-perturbative treatment of the tail ions in the interface region where the Gamow ion Knudsen number approaches or surpasses order unity. The accuracy of the coupling scheme is controlled by the precise criteria for matching the non-perturbative kinetic model to perturbative solutions in both configuration space and velocity space.

  12. Simulating galaxy formation with black hole driven thermal and kinetic feedback

    CERN Document Server

    Weinberger, Rainer; Hernquist, Lars; Pillepich, Annalisa; Marinacci, Federico; Pakmor, Rüdiger; Nelson, Dylan; Genel, Shy; Vogelsberger, Mark; Naiman, Jill; Torrey, Paul

    2016-01-01

    The inefficiency of star formation in massive elliptical galaxies is widely believed to be caused by the interactions of an active galactic nucleus (AGN) with the surrounding gas. Achieving a sufficiently rapid reddening of moderately massive galaxies without expelling too many baryons has however proven difficult for hydrodynamical simulations of galaxy formation, prompting us to explore a new model for the accretion and feedback effects of supermassive black holes. For high accretion rates relative to the Eddington limit, we assume that a fraction of the accreted rest mass energy heats the surrounding gas thermally, similar to the `quasar mode' in previous work. For low accretion rates, we invoke a new, pure kinetic feedback model which imparts momentum into the surrounding gas in a stochastic manner. These two modes of feedback are motivated both by theoretical conjectures for the existence of different types of accretion flows as well as recent observational evidence for the importance of kinetic AGN wind...

  13. Kinetic Monte Carlo simulations of surface reactions on supported nanoparticles: A novel approach and computer code

    Science.gov (United States)

    Kunz, Lothar; Kuhn, Frank M.; Deutschmann, Olaf

    2015-07-01

    So far most kinetic Monte Carlo (kMC) simulations of heterogeneously catalyzed gas phase reactions were limited to flat crystal surfaces. The newly developed program MoCKA (Monte Carlo Karlsruhe) combines graph-theoretical and lattice-based principles to be able to efficiently handle multiple lattices with a large number of sites, which account for different facets of the catalytic nanoparticle and the support material, and pursues a general approach, which is not restricted to a specific surface or reaction. The implementation uses the efficient variable step size method and applies a fast update algorithm for its process list. It is shown that the analysis of communication between facets and of (reverse) spillover effects is possible by rewinding the kMC simulation. Hence, this approach offers a wide range of new applications for kMC simulations in heterogeneous catalysis.

  14. Kinetic simulations and reduced modeling of longitudinal sideband instabilities in non-linear electron plasma waves

    Energy Technology Data Exchange (ETDEWEB)

    Brunner, S. [Centre de Recherches en Physique des Plasmas, Association Euratom-Confédération Suisse, Ecole Polytechnique Fédérale de Lausanne, Lausanne, (Switzerland); Berger, R. L. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Cohen, B. I. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Hausammann, L. [Centre de Recherches en Physique des Plasmas, Association Euratom-Confédération Suisse, Ecole Polytechnique Fédérale de Lausanne, Lausanne, (Switzerland); Valeo, E. J. [Princeton Plasma Physics Lab. (PPPL), Princeton, NJ (United States)

    2014-10-01

    Kinetic Vlasov simulations of one-dimensional finite amplitude Electron Plasma Waves are performed in a multi-wavelength long system. A systematic study of the most unstable linear sideband mode, in particular its growth rate γ and quasi- wavenumber δk, is carried out by scanning the amplitude and wavenumber of the initial wave. Simulation results are successfully compared against numerical and analytical solutions to the reduced model by Kruer et al. [Phys. Rev. Lett. 23, 838 (1969)] for the Trapped Particle Instability (TPI). A model recently suggested by Dodin et al. [Phys. Rev. Lett. 110, 215006 (2013)], which in addition to the TPI accounts for the so-called Negative Mass Instability because of a more detailed representation of the trapped particle dynamics, is also studied and compared with simulations.

  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. Simulation studies on shape and growth kinetics for fractal aggregates in aerosol and colloidal systems

    Science.gov (United States)

    Heinson, William Raymond

    The aim of this work is to explore, using computational techniques that simulate the motion and subsequent aggregation of particles in aerosol and colloidal systems, many common but not well studied systems that form fractal clusters. Primarily the focus is on cluster shape and growth kinetics. The structure of clusters made under diffusion limited cluster-cluster aggregation (DLCA) is looked at. More specifically, the shape anisotropy is found to have an inverse relationship on the scaling prefactor k0 and have no effect on the fractal dimension Df . An analytical model that predicts the shape and fractal dimension of diffusion limited cluster-cluster aggregates is tested and successfully predicts cluster shape and dimensionality. Growth kinetics of cluster-cluster aggregation in the free molecular regime where the system starts with ballistic motion and then transitions to diffusive motion as the aggregates grow in size is studied. It is shown that the kinetic exponent will crossover from the ballistic to the diffusional values and the onset of this crossover is predicted by when the nearest neighbor Knudsen number reaches unity. Simulations were carried out for a system in which molten particles coalesce into spheres, then cool till coalescing stops and finally the polydispersed monomers stick at point contacts to form fractal clusters. The kinetic exponent and overall cluster structure for these aggregates was found to be in agreement with DLCA that started with monodispersed monomers. Colloidal aggregation in the presence of shear was studied in detail. Study of a colloidal system characterized a by short-range attractive potential showed that weak shear enhanced the aggregation process. Strong shear led to fragmentation and subsequent nucleation as cluster growth rebounded after an induction time.

  17. Spectroscopic Studies of Azide compounds: Thermochemistry, Chemical Kinetics and Photodissociation Dynamics

    Science.gov (United States)

    Quinto Hernandez, Alfredo

    Some of the most difficult chemical systems, either to observe or produce in significant quantities, are polynitrogen molecules. One example of this type of molecules in the early stages of investigation is cyclic-N3, whose molecular geometry and promising technological applications have attracted our attention to define optimal experimental conditions for being photoproduced. High-resolution synchrotron-radiation-based Photoionization Mass Spectrometry (PIMS) was applied to study the dissociative photoionization of three azide precursors for cyclic-N3; chlorine azide (ClN3), hydrogen azide (HN3), and methyl azide (CH3N3). In our attempts to detect cyclic-N3, the thermochemistry derived in the PIMS studies stimulated our work to perform photodissociation dynamics experiments of CH3N3 at 193 nm using Photofragment Translational Spectroscopy (PTS) with electron impact (EI) detection under collision-free conditions, and chemical kinetic studies based on Infrared Spectroscopy (IR) in matrix-isolated ices formed from rare gases (Argon, Nitrogen and Xenon). PTS experiments lead us to derive the branching ratio between reactions CH 3+N3 (radical channel) vs CH3N+N2 (molecular channel), and to conclude that cyclic-N3 is the dominant product in the radical channel. In contrast, in the matrix isolation experiments we found no evidence of the radical channel, possibly due to barrier-less recombination. However, since no mechanistic reports of methyl azide dissociation exist at these conditions, these studies could have significant implications for future experiments addressed to detect cylic-N3 under matrix environments.

  18. Monte-Carlo simulation for fragment mass and kinetic energy distributions from neutron induced fission of 235U

    CERN Document Server

    Montoya, M; Rojas, J

    2007-01-01

    The mass and kinetic energy distribution of nuclear fragments from thermal neutron induced fission of 235U have been studied using a Monte-Carlo simulation. Besides reproducing the pronounced broadening on the standard deviation of the final fragment kinetic energy distribution $\\sigma_{e}(m)$ around the mass number m = 109, our simulation also produces a second broadening around m = 125, that is in agreement with the experimental data obtained by Belhafaf et al. These results are consequence of the characteristics of the neutron emission, the variation in the primary fragment mean kinetic energy and the yield as a function of the mass.

  19. 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.

  20. A path flux analysis method for the reduction of detailed chemical kinetic mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Sun, Wenting; Ju, Yiguang [Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 08544 (United States); Chen, Zheng [State Key Laboratory for Turbulence and Complex Systems, College of Engineering, Peking University, Beijing 100871 (China); Gou, Xiaolong [School of Power Engineering, Chongqing University, Chongqing 400044 (China)

    2010-07-15

    A direct path flux analysis (PFA) method for kinetic mechanism reduction is proposed and validated by using high temperature ignition, perfect stirred reactors, and steady and unsteady flame propagations of n-heptane and n-decane/air mixtures. The formation and consumption fluxes of each species at multiple reaction path generations are analyzed and used to identify the important reaction pathways and the associated species. The formation and consumption path fluxes used in this method retain flux conservation information and are used to define the path indexes for the first and the second generation reaction paths related to a targeted species. Based on the indexes of each reaction path for the first and second generations, different sized reduced chemical mechanisms which contain different number of species are generated. The reduced mechanisms of n-heptane and n-decane obtained by using the present method are compared to those generated by the direct relation graph (DRG) method. The reaction path analysis for n-decane is conducted to demonstrate the validity of the present method. The comparisons of the ignition delay times, flame propagation speeds, flame structures, and unsteady spherical flame propagation processes showed that with either the same or significantly less number of species, the reduced mechanisms generated by the present PFA are more accurate than that of DRG in a broad range of initial pressures and temperatures. The method is also integrated with the dynamic multi-timescale method and a further increase of computation efficiency is achieved. (author)

  1. 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.

  2. 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

  3. Metal adsorption by agricultural biosorbents: Adsorption isotherm, kinetic and biosorbents chemical structures.

    Science.gov (United States)

    Sadeek, Sadeek A; Negm, Nabel A; Hefni, Hassan H H; Wahab, Mostafa M Abdel

    2015-11-01

    Biosorption of Cu(II), Co(II) and Fe(III) ions from aqueous solutions by rice husk, palm leaf and water hyacinth was investigated as a function of initial pH, initial heavy metal ions concentration and treatment time. The adsorption process was examined by two adsorption isotherms: Langmuir and Freundlich isotherms. The experimental data of biosorption process were analyzed using pseudo-first order, pseudo-second order kinetic models. The equilibrium biosorption isotherms showed that the three studied biosorbents possess high affinity and sorption capacity for Cu(II), Co(II) and Fe(III) ions. Rice husk showed more efficiency than palm leaf and water hyacinth. Adsorption of Cu(II) and Co(II) was more efficient in alkaline medium (pH 9) than neutral medium due to the high solubility of metal ion complexes. The metal removal efficiency of each biosorbent was correlated to its chemical structure. DTA studies showed formation of metal complex between the biosorbents and the metal ions. The obtained results showed that the tested biosorbents are efficient and alternate low-cost biosorbent for removal of heavy metal ions from aqueous media. PMID:26282929

  4. Development of a hydro kinetic river turbine with simulation and operational measurement results in comparison

    Science.gov (United States)

    Ruopp, A.; Ruprecht, A.; Riedelbauch, S.; Arnaud, G.; Hamad, I.

    2014-03-01

    The development of a hydro-kinetic prototype was shown including the compound structure, guide vanes, runner blades and a draft tube section with a steeply sloping, short spoiler. The design process of the hydrodynamic layout was split into three major steps. First the compound and the draft tube section was designed and the best operating point was identified using porous media as replacement for the guide vane and runner section (step one). The best operating point and the volume flux as well as the pressure drop was identified and used for the design of the guide vane section and the runner section. Both were designed and simulated independently (step two). In step three, all parts were merged in stationary simulation runs detecting peak power and operational bandwidth. In addition, the full scale demonstrator was installed in August 2010 and measured in the St. Lawrence River in Quebec supporting the average inflow velocity using ADCP (Acoustic Doppler Current Profiler) and the generator power output over the variable rotational speed. Simulation data and measurements are in good agreement. Thus, the presented approach is a suitable way in designing a hydro kinetic turbine.

  5. Observed and Simulated Power Spectra of Kinetic and Magnetic Energy retrieved with 2D inversions

    CERN Document Server

    Danilovic, S; van Noort, M; Cameron, R

    2016-01-01

    We try to retrieve the power spectra with certainty to the highest spatial frequencies allowed by current instrumentation. For this, we use 2D inversion code that were able to recover information up to the instrumental diffraction limit. The retrieved power spectra have shallow slopes extending further down to much smaller scales than found before. They seem not to show any power law. The observed slopes at subgranular scales agree with those obtained from recent local dynamo simulations. Small differences are found for vertical component of kinetic energy that suggest that observations suffer from an instrumental effect that is not taken into account.

  6. A kinetic neutral atom model for tokamak scrape-off layer tubulence simulations

    OpenAIRE

    Wersal, Christoph; Ricci, Paolo; Halpern, Federico David; Riva, Fabio

    2014-01-01

    The first-principle understanding of the processes in the Scrape-Off-Layer (SOL) of a tokamak is crucial for the developement of a thermonuclear re- actor. Since the plasma temperature in the SOL is rather low, the plasma is typically not fully ionized, and the neutral atoms play an important role in determining the SOL regimes. The description of a simple kinetic model for neutral atoms in the SOL is presented and first results of self-consistent non-linear turbulence simulations with the GB...

  7. Interplay between density profile and zonal flows in drift kinetic simulations of slab ITG turbulence

    International Nuclear Information System (INIS)

    This paper reports on 4-dimensional drift kinetic simulations of the slab branch of the Ion Temperature Gradient driven turbulence in a cylinder. In the non-linear regime, the system is found to relax preferentially either via heat transport or via mean sheared flows, depending on the density profile. A strong density gradient appears to be stabilizing both linearly, by increasing the instability threshold, and non linearly, by activating sheared flows. This impedes the relaxation of the profiles and sustains a pressure transport barrier. (author)

  8. Interplay between density profile and zonal flows in drift kinetic simulations of slab ITG turbulence

    International Nuclear Information System (INIS)

    This paper reports on 4-dimensional drift kinetic simulations of the slab branch of the Ion Temperature Gradient driven turbulence in a cylinder. In the non-linear regime, the system is found to relax preferentially either via heat transport or via mean sheared flows, depending on the density profile. A strong density gradient appears to be stabilizing both linearly, by increasing the instability threshold, and non linearly, by activating sheared flows. This impedes the relaxation of the profiles and sustains a pressure transport barrier. (authors)

  9. Simulation of aerosol chemical compositions in the Western Mediterranean Sea

    Science.gov (United States)

    Chrit, Mounir; Kata Sartelet, Karine; Sciare, Jean; Marchand, Nicolas; Pey, Jorge; Sellegri, Karine

    2016-04-01

    This work aims at evaluating the chemical transport model (CTM) Polair3d of the air-quality modelling platform Polyphemus during the ChArMex summer campaigns of 2013, using ground-based measurements performed at ERSA (Cape Corsica, France), and at determining the processes controlling organic aerosol concentrations at ERSA. Simulations are compared to measurements for concentrations of both organic and inorganic species, as well as the ratio of biogenic versus anthropogenic particles, and organic aerosol properties (oxidation state). For inorganics, the concentrations of sulphate, sodium, chloride, ammonium and nitrate are compared to measurements. Non-sea-salt sulphate and ammonium concentrations are well reproduced by the model. However, because of the geographic location of the measurement station at Cape Corsica which undergoes strong wind velocities and sea effects, sea-salt sulphate, sodium, chloride and nitrate concentrations are strongly influenced by the parameterizations used for sea-salt emissions. Different parameterizations are compared and a parameterization is chosen after comparison to sodium measurements. For organics, the concentrations are well modelled when compared to experimental values. Anthropogenic particles are influenced by emission of semi-volatile organic compounds (SVOC). Measurements allow us to refine the estimation of those emissions, which are currently missing in emission inventories. Although concentrations of biogenic particles are well simulated, the organic chemical compounds are not enough oxidised in the model. The observed oxidation state of organics shows that the oligomerisation of pinonaldehyde was over-estimated in Polyphemus. To improve the oxidation property of organics, the formation of extremely low volatile organic compounds from autoxidation of monoterpenes is added to Polyphemus, using recently published data from chamber experiments. These chemical compounds are highly oxygenated and are formed rapidly, as first

  10. Chemical evolution of giant molecular clouds in simulations of galaxies

    Science.gov (United States)

    Richings, Alexander J.; Schaye, Joop

    2016-08-01

    We present an analysis of Giant Molecular Clouds (GMCs) within hydrodynamic simulations of isolated, low-mass (M* ~ 10^9 M_sol) disc galaxies. We study the evolution of molecular abundances and the implications for CO emission and the X_CO conversion factor in individual clouds. We define clouds either as regions above a density threshold n_H,min = 10 cm^-3, or using an observationally motivated CO intensity threshold of 0.25 K km s^-1. Our simulations include a non-equilibrium chemical model with 157 species, including 20 molecules. We also investigate the effects of resolution and pressure floors (i.e. Jeans limiters). We find cloud lifetimes up to ~40 Myr, with a median of 13 Myr, in agreement with observations. At one tenth solar metallicity, young clouds (<10-15 Myr) are underabundant in H2 and CO compared to chemical equilibrium, by factors of ~3 and 1-2 orders of magnitude, respectively. At solar metallicity, GMCs reach chemical equilibrium faster (within ~1 Myr). We also compute CO emission from individual clouds. The mean CO intensity, I_CO, is strongly suppressed at low dust extinction, A_v, and possibly saturates towards high A_v, in agreement with observations. The I_CO - A_v relation shifts towards higher A_v for higher metallicities and, to a lesser extent, for stronger UV radiation. At one tenth solar metallicity, CO emission is weaker in young clouds (<10-15 Myr), consistent with the underabundance of CO. Consequently, X_CO decreases by an order of magnitude from 0 to 15 Myr, albeit with a large scatter.

  11. 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...

  12. KINETIC MONTE CARLO SIMULATIONS OF THE EFFECTS OF 1-D DEFECT TRANSPORT ON DEFECT REACTION KINETICS AND VOID LATTICE FORMATION DURING IRRADIATION

    International Nuclear Information System (INIS)

    Within the last decade molecular dynamics simulations of displacement cascades have revealed that glissile clusters of self-interstitial crowdions are formed directly in cascades. Also, under various conditions, a crowdion cluster can change its Burgers vector and glide along a different close-packed direction. In order to incorporate the migration properties of crowdion clusters into analytical rate theory models, it is necessary to describe the reaction kinetics of defects that migrate one-dimensionally with occasional changes in their Burgers vector. To meet this requirement, atomic-scale kinetic Monte Carlo (KMC) simulations have been used to study the defect reaction kinetics of one-dimensionally migrating crowdion clusters as a function of the frequency of direction changes, specifically to determine the sink strengths for such one-dimensionally migrating defects. The KMC experiments are used to guide the development of analytical expressions for use in reaction rate theories and especially to test their validity. Excellent agreement is found between the results of KMC experiments and the analytical expressions derived for the transition from one-dimensional to three-dimensional reaction kinetics. Furthermore, KMC simulations have been performed to investigate the significant role of crowdion clusters in the formation and stability of void lattices. The necessity for both one-dimensional migration and Burgers vectors changes for achieving a stable void lattice is demonstrated.

  13. Simulation of nucleation kinetics of radiation-induced defect clusters in irradiated materials

    International Nuclear Information System (INIS)

    A numerical method for simulation kinetics of radiation-induced defect clusters in irradiated materials is developed. Calculations of nucleation kinetics of radiation-induced defect clusters under pulsed irradiation corresponding to continuous irradiation of the thermonuclear reactor first wall are carried out. It is shown that under pulsed irradiation the concentration of nucleated dislocation loops doesn't practically differ from the concentration of loops nucleated at the same doses under continuous irradiation. The average size of dislocation loops nucleated under cyclic irradiation (τ1=103 s, τ2=103 s) at radiation time τ=2x104 s is two times less than the average size of dislocation loops nucleated at the same time of continuous irradiation. Comparative analysis of nucleation kinetics of radiation-induced defect clusters is carried out for two models of linear dislocations: dislocations, being a ''continuous'' sink for point defects, and dislocations, being ''discrete'' sink for them. Account of microscopic processes occuring in dislocation nuclei (a model of ''discrete'' dislocation) is shown to lead to faster rates of nucleation and growth of dislocation loops, which values are similar to the values experimentally observed

  14. Kinetic AGN Feedback Effects on Cluster Cool Cores Simulated using SPH

    CERN Document Server

    Barai, Paramita; Borgani, Stefano; Gaspari, Massimo; Granato, Gian Luigi; Monaco, Pierluigi; Ragone-Figueroa, Cinthia

    2016-01-01

    We implement novel numerical models of AGN feedback in the SPH code GADGET-3, where the energy from a supermassive black hole (BH) is coupled to the surrounding gas in the kinetic form. Gas particles lying inside a bi-conical volume around the BH are imparted a one-time velocity (10,000 km/s) increment. We perform hydrodynamical simulations of isolated cluster (total mass 10^14 /h M_sun), which is initially evolved to form a dense cool core, having central T<10^6 K. A BH resides at the cluster center, and ejects energy. The feedback-driven fast wind undergoes shock with the slower-moving gas, which causes the imparted kinetic energy to be thermalized. Bipolar bubble-like outflows form propagating radially outward to a distance of a few 100 kpc. The radial profiles of median gas properties are influenced by BH feedback in the inner regions (r<20-50 kpc). BH kinetic feedback, with a large value of the feedback efficiency, depletes the inner cool gas and reduces the hot gas content, such that the initial c...

  15. Numerical simulations of subcritical reactor kinetics in thermal hydraulic transient phases

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, J.; Park, W. S. [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

    1998-12-31

    A subcritical reactor driven by a linear proton accelerator has been considered as a nuclear waste incinerator at Korea Atomic Energy Research Institute (KAERI). Since the multiplication factor of a subcritical reactor is less than unity, to compensate exponentially decreasing fission neutrons, external neutrons form spallation reactions are essentially required for operating the reactor in its steady state. Furthermore, the profile of accelerator beam currents is very important in controlling a subcritical reactor, because the reactor power varies in accordance to the profile of external neutrons. We have developed a code system to find numerical solutions of reactor kinetics equations, which are the simplest dynamic model for controlling reactors. In a due course of our previous numerical study of point kinetics equations for critical reactors, however, we learned that the same code system can be used in studying dynamic behavior of the subcritical reactor. Our major motivation of this paper is to investigate responses of subcritical reactors for small changes in thermal hydraulic parameters. Building a thermal hydraulic model for the subcritical reactor dynamics, we performed numerical simulations for dynamic responses of the reactor based on point kinetics equations with a source term. Linearizing a set of coupled differential equations for reactor responses, we focus our research interest on dynamic responses of the reactor to variations of the thermal hydraulic parameters in transient phases. 5 refs., 8 figs. (Author)

  16. Kinetic Cooperativity, Loop Dynamics, and Allostery from NMR and MD simulations

    Science.gov (United States)

    Bruschweiler, Rafael

    The hallmark of glucokinase (GCK), which catalyzes the phosphorylation of glucose during glycolysis, is its kinetic cooperativity whose understanding at atomic detail has remained open since its discovery over 40 years ago. I will discuss how the origin of kinetic cooperativity is rooted in intramolecular protein dynamics using NMR relaxation data of 17 isoleucines distributed over all parts of GCK. Residues of glucose-free GCK located in the small domain display a distinct exchange behavior involving multiple conformers that are substantially populated, whereas in the glucose-bound form these dynamic processes are quenched. The conformational exchange process directly competes with the enzymatic turnover at physiological glucose concentrations, thereby generating the sigmoidal rate dependence that defines kinetic cooperativity. The flexible nature of protein loops and the timescales of their dynamics are critical for many biologically important events at the molecular level, such as protein interaction and recognition processes. Based on a library of proteins, rules about loop dynamics in terms of amplitude and timescales can be derived using molecular dynamics (MD) simulations and NMR data. These rules have been implemented in the new web server ToeLoop (for Timescales Of Every Loop) that permits the prediction of loop dynamics based on an average 3D protein structure (http://spin.ccic.ohio-state.edu/index.php/loop/index).

  17. A higher-order numerical framework for stochastic simulation of chemical reaction systems.

    KAUST Repository

    Székely, Tamás

    2012-07-15

    BACKGROUND: In this paper, we present a framework for improving the accuracy of fixed-step methods for Monte Carlo simulation of discrete stochastic chemical kinetics. Stochasticity is ubiquitous in many areas of cell biology, for example in gene regulation, biochemical cascades and cell-cell interaction. However most discrete stochastic simulation techniques are slow. We apply Richardson extrapolation to the moments of three fixed-step methods, the Euler, midpoint and θ-trapezoidal τ-leap methods, to demonstrate the power of stochastic extrapolation. The extrapolation framework can increase the order of convergence of any fixed-step discrete stochastic solver and is very easy to implement; the only condition for its use is knowledge of the appropriate terms of the global error expansion of the solver in terms of its stepsize. In practical terms, a higher-order method with a larger stepsize can achieve the same level of accuracy as a lower-order method with a smaller one, potentially reducing the computational time of the system. RESULTS: By obtaining a global error expansion for a general weak first-order method, we prove that extrapolation can increase the weak order of convergence for the moments of the Euler and the midpoint τ-leap methods, from one to two. This is supported by numerical simulations of several chemical systems of biological importance using the Euler, midpoint and θ-trapezoidal τ-leap methods. In almost all cases, extrapolation results in an improvement of accuracy. As in the case of ordinary and stochastic differential equations, extrapolation can be repeated to obtain even higher-order approximations. CONCLUSIONS: Extrapolation is a general framework for increasing the order of accuracy of any fixed-step stochastic solver. This enables the simulation of complicated systems in less time, allowing for more realistic biochemical problems to be solved.

  18. 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.

  19. 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.

  20. Towards Quantum Simulation of Chemical Dynamics with Prethreshold Superconducting Qubits

    CERN Document Server

    Stancil, P C; Cook, A; Sornborger, A T; Geller, M R

    2016-01-01

    The single excitation subspace (SES) method for universal quantum simulation is investigated for a number of diatomic molecular collision complexes. Assuming a system of $n$ tunably-coupled, and fully-connected superconducting qubits, computations are performed in the $n$-dimensional SES which maps directly to an $n$-channel collision problem within a diabatic molecular wave function representation. Here we outline the approach on a classical computer to solve the time-dependent Schr\\"odinger equation in an $n$-dimensional molecular basis - the so-called semiclassical molecular-orbital close-coupling (SCMOCC) method - and extend the treatment beyond the straight-line, constant-velocity approximation which is restricted to large kinetic energies ($\\gtrsim 0.1$ keV/u). We explore various multichannel potential averaging schemes and an Ehrenfest symmetrization approach to allow for the application of the SCMOCC method to much lower collision energies (approaching 1 eV/u). In addition, a computational efficiency ...

  1. Self-learning kinetic Monte Carlo simulations of Al diffusion in Mg

    Science.gov (United States)

    Nandipati, Giridhar; Govind, Niranjan; Andersen, Amity; Rohatgi, Aashish

    2016-04-01

    Vacancy-mediated diffusion of an Al atom in the pure Mg matrix is studied using the atomistic, on-lattice self-learning kinetic Monte Carlo (SLKMC) method. Activation barriers for vacancy-Mg and vacancy-Al atom exchange processes are calculated on the fly using the climbing image nudged-elastic-band method and binary Mg-Al modified embedded-atom method interatomic potential. Diffusivities of an Al atom obtained from SLKMC simulations show the same behavior as observed in experimental and theoretical studies available in the literature; that is, an Al atom diffuses faster within the basal plane than along the c-axis. Although the effective activation barriers for an Al atom diffusion from SLKMC simulations are close to experimental and theoretical values, the effective prefactors are lower than those obtained from experiments. We present all the possible vacancy-Mg and vacancy-Al atom exchange processes and their activation barriers identified in SLKMC simulations. A simple mapping scheme to map an HCP lattice onto a simple cubic lattice is described, which enables simulation of the HCP lattice using the on-lattice framework. We also present the pattern recognition scheme which is used in SLKMC simulations to identify the local Al atom configuration around a vacancy.

  2. Self-Learning Kinetic Monte Carlo Simulations of Al Diffusion in Mg

    Energy Technology Data Exchange (ETDEWEB)

    Nandipati, Giridhar; Govind, Niranjan; Andersen, Amity; Rohatgi, Aashish

    2016-03-16

    Atomistic on-lattice self-learning kinetic Monte Carlo (SLKMC) method was used to examine the vacancy-mediated diffusion of an Al atom in pure hcp Mg. Local atomic environment dependent activation barriers for vacancy-atom exchange processes were calculated on-the-fly using climbing image nudged-elastic band method (CI-NEB) and using a Mg-Al binary modified embedded-atom method (MEAM) interatomic potential. Diffusivities of vacancy and Al atom in pure Mg were obtained from SLKMC simulations and are compared with values available in the literature that are obtained from experiments and first-principle calculations. Al Diffusivities obtained from SLKMC simulations are lower, due to larger activation barriers and lower diffusivity prefactors, than those available in the literature but have same order of magnitude. We present all vacancy-Mg and vacancy-Al atom exchange processes and their activation barriers that were identified in SLKMC simulations. We will describe a simple mapping scheme to map a hcp lattice on to a simple cubic lattice that would enable hcp lattices to be simulated in an on-lattice KMC framework. We also present the pattern recognition scheme used in SLKMC simulations.

  3. Self-learning kinetic Monte Carlo simulations of Al diffusion in Mg

    International Nuclear Information System (INIS)

    Vacancy-mediated diffusion of an Al atom in the pure Mg matrix is studied using the atomistic, on-lattice self-learning kinetic Monte Carlo (SLKMC) method. Activation barriers for vacancy-Mg and vacancy-Al atom exchange processes are calculated on the fly using the climbing image nudged-elastic-band method and binary Mg–Al modified embedded-atom method interatomic potential. Diffusivities of an Al atom obtained from SLKMC simulations show the same behavior as observed in experimental and theoretical studies available in the literature; that is, an Al atom diffuses faster within the basal plane than along the c-axis. Although the effective activation barriers for an Al atom diffusion from SLKMC simulations are close to experimental and theoretical values, the effective prefactors are lower than those obtained from experiments. We present all the possible vacancy-Mg and vacancy-Al atom exchange processes and their activation barriers identified in SLKMC simulations. A simple mapping scheme to map an HCP lattice onto a simple cubic lattice is described, which enables simulation of the HCP lattice using the on-lattice framework. We also present the pattern recognition scheme which is used in SLKMC simulations to identify the local Al atom configuration around a vacancy. (paper)

  4. 3D Kinetic Simulations of Topography-Induced Electric Fields at Itokawa Asteroid

    Science.gov (United States)

    Zimmerman, M. I.

    2015-12-01

    Results from a new 3D kinetic simulation code will be presented, showing how Itokawa's interaction with the solar wind plasma creates an ever-evolving electric field structure as the asteroid rotates. The simulations combine (1) a realistic surface shape model of Itokawa, (2) a careful and self-consistent accounting of surface charging processes, and (3) the freely-available FMMLib3d code library implementing the fast multipole method for electric field calculations. Fine details of the surface potential and electric grounding conditions, as revealed by this new code, could provide critical inputs into planning for a future asteroid retrieval mission in which extended, direct contact with the asteroid could occur.

  5. R\\^ole of kinetic transport coefficients for hydrodynamic simulations of granular flow

    CERN Document Server

    Almazán, Lidia; Salueña, Clara; Garzó, Vicente; Pöschel, Thorsten

    2012-01-01

    A numerical study is presented to assess the performance of two different models of kinetic transport coefficients for granular materials, namely the Jenkins-Richman theory for moderately dense, quasielastic grains, and the improved Lutsko-Garz\\'o theory for arbitrary inelasticity. For this purpose a time-dependent problem such as the granular Faraday instability is selected to perform numerical simulations of the granular Navier-Stokes equations. Both solutions are compared with event-driven simulations of the same system under the same conditions, by analyzing the density, the temperature and the velocity field. Important differences are found between the two models leading to interesting implications. In particular the heat transfer mechanism coupled to the density gradient which is a distinctive feature of inelastic granular gases, is responsible for a major discrepancy in the temperature field and hence in the diffusion mechanisms.

  6. Kinetic Monte Carlo and Cellular Particle Dynamics Simulations of Multicellular Systems

    CERN Document Server

    Flenner, Elijah; Barz, Bogdan; Neagu, Adrian; Forgacs, Gabor; Kosztin, Ioan

    2011-01-01

    Computer modeling of multicellular systems has been a valuable tool for interpreting and guiding in vitro experiments relevant to embryonic morphogenesis, tumor growth, angiogenesis and, lately, structure formation following the printing of cell aggregates as bioink particles. Computer simulations based on Metropolis Monte Carlo (MMC) algorithms were successful in explaining and predicting the resulting stationary structures (corresponding to the lowest adhesion energy state). Here we introduce two alternatives to the MMC approach for modeling cellular motion and self-assembly: (1) a kinetic Monte Carlo (KMC), and (2) a cellular particle dynamics (CPD) method. Unlike MMC, both KMC and CPD methods are capable of simulating the dynamics of the cellular system in real time. In the KMC approach a transition rate is associated with possible rearrangements of the cellular system, and the corresponding time evolution is expressed in terms of these rates. In the CPD approach cells are modeled as interacting cellular ...

  7. The validity of the kinetic collection equation revisited – Part 2: Simulations for the hydrodynamic kernel

    Directory of Open Access Journals (Sweden)

    L. Alfonso

    2010-08-01

    Full Text Available The kinetic collection equation (KCE has been widely used to describe the evolution of the average droplet spectrum due to the collection process that leads to the development of precipitation in warm clouds. This deterministic, integro-differential equation only has analytic solution for very simple kernels. For more realistic kernels, the KCE needs to be integrated numerically. In this study, the validity time of the KCE for the hydrodynamic kernel is estimated by a direct comparison of Monte Carlo simulations with numerical solutions of the KCE. The simulation results show that when the largest droplet becomes separated from the smooth spectrum, the total mass calculated from the numerical solution of the KCE is not conserved and, thus, the KCE is no longer valid. This result confirms the fact that for kernels appropriate for precipitation development within warm clouds, the KCE can only be applied to the continuous portion of the mass distribution.

  8. The validity of the kinetic collection equation revisited – Part 2: Simulations for the hydrodynamic kernel

    Directory of Open Access Journals (Sweden)

    L. Alfonso

    2010-03-01

    Full Text Available The kinetic collection equation (KCE has been widely used to describe the evolution of the average droplet spectrum due to the collection process that leads to the development of precipitation in warm clouds. This deterministic, integro-differential equation only has analytic solution for very simple kernels. For more realistic kernels, the KCE needs to be integrated numerically. In this study, the validity time of the KCE for the hydrodynamic kernel is estimated by a direct comparison of Monte Carlo simulations with numerical solutions of the KCE. The simulation results show that when the largest droplet becomes separated from the smooth spectrum, the total mass calculated from the numerical solution of the KCE is not conserved and, thus, the KCE is no longer valid. This result confirms the fact that for realistic kernels appropriate for precipitation development within warm clouds, the KCE can only be applied to the continuous portion of the mass distribution.

  9. Extended pattern recognition scheme for self-learning kinetic Monte Carlo simulations

    International Nuclear Information System (INIS)

    We report the development of a pattern recognition scheme that takes into account both fcc and hcp adsorption sites in performing self-learning kinetic Monte Carlo (SLKMC-II) simulations on the fcc(111) surface. In this scheme, the local environment of every under-coordinated atom in an island is uniquely identified by grouping fcc sites, hcp sites and top-layer substrate atoms around it into hexagonal rings. As the simulation progresses, all possible processes, including those such as shearing, reptation and concerted gliding, which may involve fcc-fcc, hcp-hcp and fcc-hcp moves are automatically found, and their energetics calculated on the fly. In this article we present the results of applying this new pattern recognition scheme to the self-diffusion of 9-atom islands (M9) on M(111), where M = Cu, Ag or Ni.

  10. Kinetic Simulation of the Electron-Cyclotron Maser Instability: Relaxation of Electron Horseshoe Distributions

    CERN Document Server

    Kuznetsov, Alexey A

    2010-01-01

    The electron-cyclotron maser instability (ECMI) is responsible for generation of the planetary auroral radio emissions. Most likely, the same mechanism produces radio bursts from ultracool dwarfs. We investigate amplification of plasma waves by the horseshoe-like electron distribution (similar to those observed in the terrestrial magnetosphere) as well as relaxation of this distribution due to the ECMI. We aim to determine parameters of the generated plasma waves, timescales of the relaxation process, and the conversion efficiency of the particle energy into waves. We have developed a kinetic relativistic quasi-linear 2D code for simulating the coevolution of an electron distribution and the high-frequency plasma waves. The code includes the processes of wave growth and particle diffusion which are assumed to be much faster than other processes (particle injection, etc.). A number of simulations have been performed for different parameter sets which seem to be typical for the magnetospheres of ultracool dwarf...

  11. Homogeneous states in driven granular mixtures: Enskog kinetic theory versus molecular dynamics simulations

    Energy Technology Data Exchange (ETDEWEB)

    Khalil, Nagi, E-mail: nagi@us.es; Garzó, Vicente, E-mail: vicenteg@unex.es [Departamento de Física, Universidad de Extremadura, E-06071 Badajoz (Spain)

    2014-04-28

    The homogeneous state of a binary mixture of smooth inelastic hard disks or spheres is analyzed. The mixture is driven by a thermostat composed by two terms: a stochastic force and a drag force proportional to the particle velocity. The combined action of both forces attempts to model the interaction of the mixture with a bath or surrounding fluid. The problem is studied by means of two independent and complementary routes. First, the Enskog kinetic equation with a Fokker-Planck term describing interactions of particles with thermostat is derived. Then, a scaling solution to the Enskog kinetic equation is proposed where the dependence of the scaled distributions φ{sub i} of each species on the granular temperature occurs not only through the dimensionless velocity c = v/v{sub 0} (v{sub 0} being the thermal velocity) but also through the dimensionless driving force parameters. Approximate forms for φ{sub i} are constructed by considering the leading order in a Sonine polynomial expansion. The ratio of kinetic temperatures T{sub 1}/T{sub 2} and the fourth-degree velocity moments λ{sub 1} and λ{sub 2} (which measure non-Gaussian properties of φ{sub 1} and φ{sub 2}, respectively) are explicitly determined as a function of the mass ratio, size ratio, composition, density, and coefficients of restitution. Second, to assess the reliability of the theoretical results, molecular dynamics simulations of a binary granular mixture of spheres are performed for two values of the coefficient of restitution (α = 0.9 and 0.8) and three different solid volume fractions (ϕ = 0.00785, 0.1, and 0.2). Comparison between kinetic theory and computer simulations for the temperature ratio shows excellent agreement, even for moderate densities and strong dissipation. In the case of the cumulants λ{sub 1} and λ{sub 2}, good agreement is found for the lower densities although significant discrepancies between theory and simulation are observed with increasing density.

  12. Kinetic structures of quasi-perpendicular shocks in global particle-in-cell simulations

    Energy Technology Data Exchange (ETDEWEB)

    Peng, Ivy Bo, E-mail: bopeng@kth.se; Markidis, Stefano; Laure, Erwin [KTH Royal Institute of Technology, Stockholm (Sweden); Johlander, Andreas; Vaivads, Andris; Khotyaintsev, Yuri [Swedish Institute of Space Physics, Uppsala (Sweden); Henri, Pierre [LPC2E-CNRS, Orléans (France); Lapenta, Giovanni [Centre for mathematical Plasma-Astrophysics, KU Leuven, Leuven (Belgium)

    2015-09-15

    We carried out global Particle-in-Cell simulations of the interaction between the solar wind and a magnetosphere to study the kinetic collisionless physics in super-critical quasi-perpendicular shocks. After an initial simulation transient, a collisionless bow shock forms as a result of the interaction of the solar wind and a planet magnetic dipole. The shock ramp has a thickness of approximately one ion skin depth and is followed by a trailing wave train in the shock downstream. At the downstream edge of the bow shock, whistler waves propagate along the magnetic field lines and the presence of electron cyclotron waves has been identified. A small part of the solar wind ion population is specularly reflected by the shock while a larger part is deflected and heated by the shock. Solar wind ions and electrons are heated in the perpendicular directions. Ions are accelerated in the perpendicular direction in the trailing wave train region. This work is an initial effort to study the electron and ion kinetic effects developed near the bow shock in a realistic magnetic field configuration.

  13. Kinetic Monte Carlo Simulation of Oxygen and Cation Diffusion in Yttria-Stabilized Zirconia

    Science.gov (United States)

    Good, Brian

    2011-01-01

    Yttria-stabilized zirconia (YSZ) is of interest to the aerospace community, notably for its application as a thermal barrier coating for turbine engine components. In such an application, diffusion of both oxygen ions and cations is of concern. Oxygen diffusion can lead to deterioration of a coated part, and often necessitates an environmental barrier coating. Cation diffusion in YSZ is much slower than oxygen diffusion. However, such diffusion is a mechanism by which creep takes place, potentially affecting the mechanical integrity and phase stability of the coating. In other applications, the high oxygen diffusivity of YSZ is useful, and makes the material of interest for use as a solid-state electrolyte in fuel cells. The kinetic Monte Carlo (kMC) method offers a number of advantages compared with the more widely known molecular dynamics simulation method. In particular, kMC is much more efficient for the study of processes, such as diffusion, that involve infrequent events. We describe the results of kinetic Monte Carlo computer simulations of oxygen and cation diffusion in YSZ. Using diffusive energy barriers from ab initio calculations and from the literature, we present results on the temperature dependence of oxygen and cation diffusivity, and on the dependence of the diffusivities on yttria concentration and oxygen sublattice vacancy concentration. We also present results of the effect on diffusivity of oxygen vacancies in the vicinity of the barrier cations that determine the oxygen diffusion energy barriers.

  14. Kinetic structures of quasi-perpendicular shocks in global particle-in-cell simulations

    International Nuclear Information System (INIS)

    We carried out global Particle-in-Cell simulations of the interaction between the solar wind and a magnetosphere to study the kinetic collisionless physics in super-critical quasi-perpendicular shocks. After an initial simulation transient, a collisionless bow shock forms as a result of the interaction of the solar wind and a planet magnetic dipole. The shock ramp has a thickness of approximately one ion skin depth and is followed by a trailing wave train in the shock downstream. At the downstream edge of the bow shock, whistler waves propagate along the magnetic field lines and the presence of electron cyclotron waves has been identified. A small part of the solar wind ion population is specularly reflected by the shock while a larger part is deflected and heated by the shock. Solar wind ions and electrons are heated in the perpendicular directions. Ions are accelerated in the perpendicular direction in the trailing wave train region. This work is an initial effort to study the electron and ion kinetic effects developed near the bow shock in a realistic magnetic field configuration

  15. Monnte Carlo Simulation of Kinetics of Ammonia Oxidative Decomposition over the Commercial Propylene Ammoxidation Catalyst(Mo-Bi)

    Institute of Scientific and Technical Information of China (English)

    罗正鸿; 詹晓力; 等

    2003-01-01

    Monte Carlo method is applied to investigate the kinetics of ammonia oxidative decomposition over the commercial propylene ammoxidation catalyst(Mo-Bi).The simulation is quite in agreement with experimetal results.Monte Carlo simulation proves that the process of ammonia oxidation decomposition is a two-step reaction.

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

    CERN Document Server

    Rimmer, Paul B

    2015-01-01

    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 K and 30000 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 HD209458b, Jupiter and the present-day Earth using a simple 1D photochemistry/diffusion code. Our results for the early Earth agree with those of Kasting (1993) 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 resul...

  17. 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

  18. FINITE ELEMENT METHOD AND ANALYSIS FOR CHEMICAL-FLOODING SIMULATION

    Institute of Scientific and Technical Information of China (English)

    YUAN Yirang

    2000-01-01

    This article discusses the enhanced oil recovery numerical simulation of the chemical-flooding (such as surfactants, alcohol, polymers) composed of three-dimensional multicomponent, multiphase and incompressible mixed fluids. The mathematical model can be described as a coupled system of nonlinear partial differential equations with initialboundary value problems. From the actual conditions such as the effect of cross interference and the three-dimensional characteristic of large-scale science-engineering computation, this article puts forward a kind of characteristic finite element fractional step schemes and obtain the optimal order error estimates in L2 norm. Thus we have thoroughly solved the well-known theoretical problem proposed by a famous scientist, R. E. Ewing.

  19. DEVELOPMENT OF HAZARDOUS SLUDGE SIMULANTS FOR ENHANCED CHEMICAL CLEANING TESTS

    Energy Technology Data Exchange (ETDEWEB)

    Eibling, R.

    2010-04-12

    An Enhanced Chemical Cleaning (ECC) process is being developed by Savannah River Remediation (SRR) to aid in Savannah River Site (SRS) High-Level Waste (HLW) tank closure. After bulk waste removal, the ECC process can be used to dissolve and remove much of the remaining sludge from HLW tanks. The ECC process uses dilute oxalic acid (1 wt %) with in-line pH monitoring and control. The resulting oxalate is decomposed through hydroxylation using an Advanced Oxidation Process (AOP). Minimizing the amount of oxalic acid used for dissolution and the subsequent oxidative destruction of oxalic acid will minimize the potential for downstream impacts. Initial efficacy tests by AREVA demonstrated that previous tank heel simulants could be dissolved using dilute oxalic acid. The oxalate could be decomposed by an AOP that utilized ozone and ultraviolet (UV) light, and the resultant metal oxides and hydroxides could be separated out of the process.

  20. 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.

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

    OpenAIRE

    M. Hamdi Karaoglu; Mehmet Uğurlu; İbrahim Kula

    2011-01-01

    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 des...

  2. 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.

  3. 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.

  4. Kinetics, simulation and insights for CO selective oxidation in fuel cell applications

    Science.gov (United States)

    Choi, Yongtaek; Stenger, Harvey G.

    The kinetics of CO preferential oxidation (PROX) was studied to evaluate various rate expressions and to simulate the performance the CO oxidation step of a methanol fuel processor for fuel cell applications. The reaction was carried out in a micro reactor testing unit using a commercial Engelhard Selectoxo (Pt-Fe/γ-alumina) catalyst and three self-prepared catalysts. Temperature was varied between 100 and 300 °C, and a of range feed rates and compositions were tested. A reaction model in which three reactions (CO oxidation, H 2 oxidation and the water gas shift reaction) occur simultaneously was chosen to predict the reactor performance. Using non-linear least squares, empirical power-law type rate expressions were found to fit the experimental data. It was critical to include all three reactions to determine good fitting results. In particular, the reverse water gas shift reaction had an important role when fitting the experimental data precisely and explained the selectivity decrease at higher reaction temperatures. Using this three reaction model, several simulation studies for a commercial PROX reactor were performed. In these simulations, the effect of O 2/CO ratio, the effect of water addition, and various non-isothermal modes of operation were evaluated. The results of the simulation were compared with corresponding experimental data and shows good agreement.

  5. Modeling charged defects, dopant diffusion and activation mechanisms for TCAD simulations using kinetic Monte Carlo

    International Nuclear Information System (INIS)

    This work will show how the kinetic Monte Carlo (KMC) technique is able to successfully model the defects and diffusion of dopants in Si-based materials for advanced microelectronic devices, especially for non-equilibrium conditions. Charge states of point defects and paired dopants are also simulated, including the dependency of the diffusivities on the Fermi level and charged particle drift coming from the electric field. The KMC method is used to simulate the diffusion of the point defects, and formation and dissolution of extended defects, whereas a quasi-atomistic approach is used to take into account the carrier densities. The simulated mechanisms include the kick-out diffusion mechanism, extended defect formation and the activation/deactivation of dopants through the formation of impurity clusters. Damage accumulation and amorphization are also taken into account. Solid phase epitaxy regrowth is included, and also the dopants redistribution during recrystallization of the amorphized regions. Regarding the charged defects, the model considers the dependencies of charge reactions, electric bias, pairing and break-up reactions according to the local Fermi level. Some aspects of the basic physical mechanisms have also been taken into consideration: how to smooth out the atomistic dopant point charge distribution, avoiding very abrupt and unphysical charge profiles and how to implement the drift of charged particles into the existing electric field. The work will also discuss the efficiency, accuracy and relevance of the method, together with its implementation in a technology computer aided design process simulator

  6. Jovian Plasma Torus Interaction with Europa: 3D Hybrid Kinetic Simulation. First results

    Science.gov (United States)

    Lipatov, A. S.; Cooper, J. F.; Paterson, W. R.; Sittler, E. C.; Hartle, R. E.; Simpson, D. G.

    2010-01-01

    The hybrid kinetic model supports comprehensive simulation of the interaction between different spatial and energetic elements of the Europa-moon-magnetosphere system with respect to variable upstream magnetic field and flux or density distributions of plasma and energetic ions, electrons, and neutral atoms. This capability is critical for improving the interpretation of the existing Europa flyby measurements from the Galileo orbiter mission, and for planning flyby and orbital measurements, (including the surface and atmospheric compositions) for future missions. The simulations are based on recent models of the atmosphere of Europa (Cassidy etal.,2007;Shematovichetal.,2005). In contrast to previous approaches with MHD simulations, the hybrid model allows us to fully take into account the finite gyro radius effect and electron pressure, and to correctly estimate the ion velocity distribution and the fluxes along the magnetic field (assuming an initial Maxwellian velocity distribution for upstream background ions).Non-thermal distributions of upstream plasma will be addressed in future work. Photoionization,electron-impact ionization, charge exchange and collisions between the ions and neutrals are also included in our model. We consider two models for background plasma:(a) with O(++) ions; (b) with O(++) and S(++) ions. The majority of O2 atmosphere is thermal with an extended cold population (Cassidyetal.,2007). A few first simulations already include an induced magnetic dipole; however, several important effects of induced magnetic fields arising from oceanic shell conductivity will be addressed in later work.

  7. Kinetic plasma simulation of ion beam extraction from an ECR ion source

    International Nuclear Information System (INIS)

    Designing optimized ECR (electron cyclotron resonance) ion beam sources can be streamlined by the accurate simulation of beam optical properties in order to predict ion extraction behavior. The complexity of these models, however, can make PIC-based simulations time-consuming. In this paper, we first describe a simple kinetic plasma finite element simulation of extraction of a proton beam from a permanent magnet hexapole ECR ion source. Second, we analyze the influence of secondary electrons generated by ion collisions in the residual gas on the space charge of a proton beam of a dual-solenoid ECR ion source. The finite element method (FEM) offers a fast modeling environment, allowing analysis of ion beam behavior under conditions of varying current density, electrode potential, and gas pressure. The new version of SCALA/TOSCA v14 permits the making of simulations in tens of minutes to a few hours on standard computer platforms without the need of particle-in-cell methods. The paper is followed by the slides of the presentation. (authors)

  8. Production and destruction of eddy kinetic energy in forced submesoscale eddy-resolving simulations

    Science.gov (United States)

    Mukherjee, Sonaljit; Ramachandran, Sanjiv; Tandon, Amit; Mahadevan, Amala

    2016-09-01

    We study the production and dissipation of the eddy kinetic energy (EKE) in a submesoscale eddy field forced with downfront winds using the Process Study Ocean Model (PSOM) with a horizontal grid resolution of 0.5 km. We simulate an idealized 100 m deep mixed-layer front initially in geostrophic balance with a jet in a domain that permits eddies within a range of O(1 km-100 km). The vertical eddy viscosities and the dissipation are parameterized using four different subgrid vertical mixing parameterizations: the k - ɛ , the KPP, and two different constant eddy viscosity and diffusivity profiles with a magnitude of O(10-2m2s-1) in the mixed layer. Our study shows that strong vertical eddy viscosities near the surface reduce the parameterized dissipation, whereas strong vertical eddy diffusivities reduce the lateral buoyancy gradients and consequently the rate of restratification by mixed-layer instabilities (MLI). Our simulations show that near the surface, the spatial variability of the dissipation along the periphery of the eddies depends on the relative alignment of the ageostrophic and geostrophic shear. Analysis of the resolved EKE budgets in the frontal region from the simulations show important similarities between the vertical structure of the EKE budget produced by the k - ɛ and KPP parameterizations, and earlier LES studies. Such an agreement is absent in the simulations using constant eddy-viscosity parameterizations.

  9. Chemical evolution of giant molecular clouds in simulations of galaxies

    CERN Document Server

    Richings, Alexander J

    2016-01-01

    We present an analysis of Giant Molecular Clouds (GMCs) identified in hydrodynamic simulations of isolated, low-mass (M* ~ 10^9 M_sol) disc galaxies, with a particular focus on the evolution of molecular abundances and the implications for CO emission and the X_CO conversion factor in individual clouds. We define clouds either as regions above a density threshold n_H,min = 10 cm^-3, or using an observationally motivated velocity-integrated CO line intensity threshold of 0.25 K km s^-1. Our simulations include a non-equilibrium treatment for the chemistry of 157 species, including 20 molecules. We use a suite of runs to carefully investigate the effects of numerical resolution and pressure floors (i.e. Jeans mass limiters). We find cloud lifetimes up to ~40 Myr, with a median of 13 Myr, in agreement with observations. At ten per cent solar metallicity, young clouds (<10-15 Myr) tend to be underabundant in H2 and CO compared to chemical equilibrium, by factors of ~3 and 1-2 orders of magnitude, respectively....

  10. Kinetic simulation of the O-X conversion process in dense magnetized plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Ali Asgarian, M. [Physics Department, Isfahan University of Technology, Isfahan (Iran, Islamic Republic of); Department of Electrical and Computer Engineering, Michigan State University, Michigan 48824-1226 (United States); Verboncoeur, J. P. [Department of Electrical and Computer Engineering, Michigan State University, Michigan 48824-1226 (United States); Parvazian, A. [Physics Department, Isfahan University of Technology, Isfahan (Iran, Islamic Republic of); Trines, R. [STFC Rutherford Appleton Laboratory, Didcot (United Kingdom)

    2013-10-15

    One scheme for heating a dense magnetized plasma core, such as in a tokamak, involves launching an ordinary (O) electromagnetic wave at the low density edge. It is converted to a reflected extraordinary (X) electromagnetic wave under certain conditions, and then transformed into an electron Bernstein wave able to reach high density regions inaccessible to most other waves. The O-X mode conversion is important in heating and diagnostic processes in different devices such as tokamaks, stellarators, and some types of pinches. The goal of this study has been to demonstrate that the kinetic particle-in-cell (PIC) scheme is suitable for modeling the O-X conversion process as the first step toward a more complete simulation of O-X-B heating. The O-X process is considered and simulated with a kinetic particle model for parameters of the TJ-II stellarator using the PIC code, XOOPIC. This code is able to model the non-monotonic density and the magnetic profile of the TJ-II stellarator. It can also statistically represent the self-consistent distribution function of the plasma, which has not been possible in previous fluid models. By considering the electric and magnetic components of launched and reflected waves, the O-mode and X-mode waves can be detected, and the O-X conversion can be demonstrated. In this work, the optimum angle for conversion efficiency, as predicted by the previous theory and experimentally confirmed, is used. Via considering the power of the launched O-mode wave and the converted X-mode wave, the efficiency of 63% for O-X conversion for the optimum theoretical launch angle of 47{sup ∘} is obtained, which is in good agreement with efficiencies computed via full-wave simulations.

  11. Monte Carlo simulation for calculation of kinetic parameters in an Accelerator Driven Subcritical TRIGA reactor

    International Nuclear Information System (INIS)

    Highlights: • Among the kinetic parameters, the most important ones are βeff and Λ. • Several methods including the Rossi-α and Feynman-α techniques, slope fit and MCNPX code have been investigated. • The Monte Carlo MCNPX code was used to simulate a geometrical model of the TRIGA core. • The results of the methods have been validated. - Abstract: In this study, noise analysis techniques including Feynman-α (variance-to-mean) and Rossi-α (correlation) and dynamic method such as slope fit method have been used to calculate effective delayed neutron fraction (βeff) and neutron reproduction time (Λ) in Accelerator Driven Subcritical TRIGA reactor. The obtained results have been compared with MCNPX code results. The relative difference between MCNPX code with Feynman-α and Rossi-α techniques and slope fit method for βeff are approximately −5.4%, 1.2%, and −10.6%, −14.8%, respectively, and also for Λ is approximately 2.1%. According to results, the noise methods can been considered ideal for detection with high efficiency and zero dead time and in the slope fit method, the decay of the delayed neutrons has been neglected and only the prompt neutrons have been taken into account. In addition, quantities simulated in the current study are validated against both the reference data and the results of MCNPX code. Therefore, the purpose of this study is to simulate the commonly used experimental methods by MCNPX code and investigate the convergence as well as accuracy of the computational results for different analysis methods in calculation of the kinetic parameters in an Accelerator Driven Subcritical TRIGA reactor

  12. Gyrokinetic-ion drift-kinetic-electron simulation of the (m = 2, n = 1) cylindrical tearing mode

    Science.gov (United States)

    Chen, Y.; Chowdhury, J.; Maksimovic, N.; Parker, S. E.; Wan, W.

    2016-05-01

    Particle-in-cell simulations of (m =2 ,n =1 ) tearing mode in cylindrical plasmas are carried out with kinetic electrons using the split-weight control-variate algorithm [Y. Chen and S. E. Parker, J. Comput. Phys. 220, 839 (2007)]. Radially, global simulation shows global mode structure in agreement with reduced-magnetohydrodynamic eigenmode calculation. Simulations of the tearing layer are verified with analytic results for the collisionless, semi-collisional, and drift-tearing mode.

  13. Numerical Simulation of Thermal-Hydrological-Mechanical-Chemical Processes during CO2 Geo-sequestration in Saline Aquifer

    Science.gov (United States)

    zhang, R.; Winterfeld, P.; Yin, X.; Wu, Y.

    2013-12-01

    The significance of thermal-hydrologic-mechanical-chemical (THMC) processes is well recognized in the operation of CO2 geo-sequestration. Geomechanical and geochemical effects may significantly change aqueous phase composition, porosity and permeability of the formation, and in turn flow and transport. The TOUGHREACT simulator (Xu et al., 2004) has the capability to quantitatively simulate multiphase fluid flow, solute transport and geochemical reactions during CO2 sequestration in saline aquifers using a sequential coupling. Using a mean stress formulation, stresses, displacements, and rock deformations due to fluid injection have been simulated by the recently developed TOUGH2-CSM (Winterfeld and Wu, 2011) to account for the geomechanical effects in CO2 sequestration in saline aquifers. Based on these previously developed numerical simulators: TOUGH-ECO2N (Pruess, 2005), TOUGHREACT, and TOUGH2-CSM, we present general mathematical formulations of the THMC processes. Two coupled computational frameworks (sequentially coupled procedure and fully coupled procedure) are developed to simulate reactive, multiphase transport of CO2 in saline aquifer with thermal and geomechanical effects; both of them model (1) fluid and heat flow, and solute transport in the aqueous phase within a three-phase mixture, (2) stresses and displacements related to the mean stress, (3) non-isothermal effects on fluid properties and reaction processes, and (4) chemical equilibrium and kinetics of fluid-rock and gas-rock interactions. A set of partial differential equations is formulated to represent the physical, mechanical and chemical processes. The accuracy of the THMC models is demonstrated using four examples with analytical solutions: (1) 1D reactive transport under chemical equilibrium conditions, (2) 1D reactive transport with chemical kinetics, (3) 1D heat conduction, and (4) 1D consolidation. Finally, the developed reactive transport models with general chemical compositions are

  14. Kinetics of methane fermentation yield in biogas reactors: Genetic variation and association with chemical composition in maize

    International Nuclear Information System (INIS)

    Maize (Zea mays L.) is the most competitive crop for methane production in Germany. Methane fermentation yield per unit of dry matter (MFY) is a determinant of methane yield, but little information is available on this trait. Our objectives were to investigate the kinetics of MFY during fermentation of maize, estimate quantitative-genetic parameters for different traits related to MFY and examine the relationship of MFY with chemical composition and silage quality. Whole-plant material of 16 inbreds and their 32 testcrosses was analyzed for MFY over 35 days of fermentation using a discontinuous laboratory assay. Data were also generated on chemical composition and in vitro digestible organic matter (IVDOM). Significant genotypic variances and high heritabilities were observed for MFY at early fermentation stages (up to 5 days) probably due to different concentrations of easily degradable chemical components. However, genotypic variances and heritability of MFY reduced as fermentation progressed, because of complete or partial degradation of all chemical components. Further, there were strong correlations of MFY with chemical components at early fermentation stages but not at later stages. Therefore, MFY at later stages, which is closer to potential MFY, does not seem to be amenable to selection. High heritability of IVDOM and its strong correlation with MFY in testcrosses indicated its possible use for preliminary or indirect selection. Keeping in view the magnitude of genetic variance that was low for MFY and high for dry matter yield (DMY), the other component of methane yield, more emphasis on breeding for DMY seems appropriate. -- Highlights: ► We investigated methane fermentation yield (MFY) of diverse germplasm of maize. ► The kinetics of MFY and its correlations with chemical composition were examined. ► Genetic variance and heritability for MFY decreased with fermentation time. ► Complete fermentation (35 d) reduced correlations of MFY with chemical

  15. Kinetic multi-layer model of gas-particle interactions in aerosols and clouds (KM-GAP: linking condensation, evaporation and chemical reactions of organics, oxidants and water

    Directory of Open Access Journals (Sweden)

    M. Shiraiwa

    2012-03-01

    Full Text Available We present a novel kinetic multi-layer model for gas-particle interactions in aerosols and clouds (KM-GAP that treats explicitly all steps of mass transport and chemical reaction of semi-volatile species partitioning between gas phase, particle surface and particle bulk. KM-GAP is based on the PRA model framework (Pöschl-Rudich-Ammann, 2007, and it includes gas phase diffusion, reversible adsorption, surface reactions, bulk diffusion and reaction, as well as condensation, evaporation and heat transfer. The size change of atmospheric particles and the temporal evolution and spatial profile of the concentration of individual chemical species can be modeled along with gas uptake and accommodation coefficients. Depending on the complexity of the investigated system and the computational constraints, unlimited numbers of semi-volatile species, chemical reactions, and physical processes can be treated, and the model shall help to bridge gaps in the understanding and quantification of multiphase chemistry and microphysics in atmospheric aerosols and clouds.

    In this study we demonstrate how KM-GAP can be used to analyze, interpret and design experimental investigations of changes in particle size and chemical composition in response to condensation, evaporation, and chemical reaction. For the condensational growth of water droplets, our kinetic model results provide a direct link between laboratory observations and molecular dynamic simulations, confirming that the accommodation coefficient of water at ~270 K is close to unity (Winkler et al., 2006. Literature data on the evaporation of dioctyl phthalate as a function of particle size and time can be reproduced, and the model results suggest that changes in the experimental conditions like aerosol particle concentration and chamber geometry may influence the evaporation kinetics and can be optimized for efficient probing of specific physical effects and parameters. With regard to oxidative

  16. 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.

  17. Thermodynamic modeling and kinetics simulation of precipitate phases in AISI 316 stainless steels

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Y., E-mail: yangying@ornl.gov [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States); Busby, J.T. [Fusion and Materials for Nuclear Systems Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States)

    2014-05-01

    This work aims at utilizing modern computational microstructural modeling tools to accelerate the understanding of phase stability in austenitic steels under extended thermal aging. Using the CALPHAD approach, a thermodynamic database OCTANT (ORNL Computational Thermodynamics for Applied Nuclear Technology), including elements of Fe, C, Cr, Ni, Mn, Mo, Si, and Ti, has been developed with a focus on reliable thermodynamic modeling of precipitate phases in AISI 316 austenitic stainless steels. The thermodynamic database was validated by comparing the calculated results with experimental data from commercial 316 austenitic steels. The developed computational thermodynamics was then coupled with precipitation kinetics simulation to understand the temporal evolution of precipitates in austenitic steels under long-term thermal aging (up to 600,000 h) at a temperature regime from 300 to 900 °C. This study discusses the effect of dislocation density and difusion coefficients on the precipitation kinetics at low temperatures, which shed a light on investigating the phase stability and transformation in austenitic steels used in light water reactors.

  18. CFD Simulation of Propane Cracking Tube Using Detailed Radical Kinetic Mechanism

    Institute of Scientific and Technical Information of China (English)

    张楠; 邱彤; 陈丙珍

    2013-01-01

    In the radiant section of cracking furnace, the thermal cracking process is highly coupled with turbulent flow, heat transfer and mass transfer. In this paper, a three-dimensional simulation of propane pyrolysis reactor tube is performed based on a detailed kinetic radical cracking scheme, combined with a comprehensive rigorous compu-tational fluid dynamics (CFD) model. The eddy-dissipation-concept (EDC) model is introduced to deal with turbu-lence-chemistry interaction of cracking gas, especially for the multi-step radical kinetics. Considering the high as-pect ratio and severe gradient phenomenon, numerical strategies such as grid resolution and refinement, stepping method and relaxation technique at different levels are employed to accelerate convergence. Large scale of radial nonuniformity in the vicinity of the tube wall is investigated. Spatial distributions of each radical reaction rate are first studied, and made it possible to identify the dominant elementary reactions. Additionally, a series of operating conditions including the feedstock feed rate, wall temperature profile and heat flux profile towards the reactor tubes are investigated. The obtained results can be used as scientific guide for further technical retrofit and operation op-timization aiming at high conversion and selectivity of pyrolysis process.

  19. Subproton-scale cascades in solar wind turbulence: driven hybrid-kinetic simulations

    CERN Document Server

    Cerri, S S; Jenko, F; Told, D; Rincon, F

    2016-01-01

    A long-lasting debate in space plasma physics concerns the nature of subproton-scale fluctuations in solar wind (SW) turbulence. Over the past decade, a series of theoretical and observational studies were presented in favor of either kinetic Alfv\\'en wave (KAW) or whistler turbulence. Here, we investigate numerically the nature of the subproton-scale turbulent cascade for typical SW parameters by means of unprecedented high-resolution simulations of forced hybrid-kinetic turbulence in two real-space and three velocity-space dimensions. Our analysis suggests that small-scale turbulence in this model is dominated by KAWs at $\\beta\\gtrsim1$ and by magnetosonic/whistler fluctuations at lower $\\beta$. The spectral properties of the turbulence appear to be in good agreement with theoretical predictions. A tentative interpretation of this result in terms of relative changes in the damping rates of the different waves is also presented. Overall, the results raise interesting new questions about the properties and va...

  20. On the hydrodynamic model of thermal escape from planetary atmospheres and its comparison with kinetic simulations

    Science.gov (United States)

    Volkov, A. N.

    2016-06-01

    Parkers' model of thermal escape implies the search of solutions of one-dimensional hydrodynamic equations for an inviscid but thermally conducting gas with a critical point and vanishing temperature far from the source. The properties of solutions of this model are studied for neutral mon- and diatomic gases with the viscosity index varying from 1/2 to 1. The domains of existence and uniqueness of solutions in terms of the source Jeans escape parameter and Knudsen number are established. The solutions are found to exist only in a narrow range of the critical point Jeans parameter. The lower and upper limits of this range correspond to solutions that are dominated by either heat conduction or adiabatic expansion. Thermal escape described by Parker's model occurs in two asymptotic regimes: the low-density (LD) regime, when escape is dominated by heat conduction, and the high-density (HD) regime, when escape is dominated by adiabatic expansion. Expressions for the mass and energy escape rates in these regimes are found theoretically. The comparison of results of hydrodynamic and kinetic simulations performed in identical conditions shows that Parker's model is capable of describing thermal escape only in the HD regime, providing decent agreement with the kinetic model in terms of the atmospheric structure below the exobase and the mass and energy escape rates. In the LD regime, Parker's model predicts a much faster drop in atmospheric temperature and less extended atmospheres, and can both over- and underestimate the escape rates in orders of magnitude.