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Chemical Kinetics (chemical + kinetics)
Selected AbstractsApplication of a simple enthalpy-based pyrolysis model in numerical simulations of pyrolysis of charring materialsFIRE AND MATERIALS, Issue 1 2010S. R. Wasan Abstract A new, simple pyrolysis model for charring materials is applied to several numerical and experimental test cases with variable externally imposed heat fluxes. The model is based on enthalpy. A piecewise linear temperature field representation is adopted, in combination with an estimate for the pyrolysis front position. Chemical kinetics are not accounted for: the pyrolysis process takes place in an infinitely thin front, at the ,pyrolysis temperature'. The evolution in time of pyrolysis gases mass flow rates and surface temperatures is discussed. The presented model is able to reproduce numerical reference results, which were obtained with the more complex moving mesh model. It performs better than the integral model. We illustrate good agreement with numerical reference results for variable thickness and boundary conditions. This reveals that the model provides good results for the entire range of thermally thin and thermally thick materials. It also shows that possible interruption of the pyrolysis process, due to excessive heat losses, is automatically predicted with the present approach. Finally, an experimental test case is considered. Copyright © 2009 John Wiley & Sons, Ltd. [source] A CFL-like constraint for the fast marching method in inhomogeneous chemical kineticsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2008Ramón Escobedo Abstract Level sets and fast marching methods are a widely used technique for problems with moving interfaces. Chemical kinetics has been recently added to this family, for the description of reaction paths and chemical waves in homogeneous media, in which the velocity of the interface is described by a given field. A more general framework must consider variable velocities due to inhomogeneities induced by chemical changes. In this case, a constraint must be satisfied for the correct use of fast marching method. We deduce an analytical expression of this constraint when the Godunov scheme is used to solve the Eikonal equation, and we present numerical simulations of a case which must be enforced to obey the constraint. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Mineral precipitation associated with vertical fault zones: the interaction of solute advection, diffusion and chemical kineticsGEOFLUIDS (ELECTRONIC), Issue 1 2007CHONGBIN ZHAO Abstract This article is concerned with chemical reactions that occur between two interacting parallel fluid flows using mixing in vertical faults as an example. Mineral precipitation associated with fluid flow in permeable fault zones results in mineralization and chemical reaction (alteration) patterns, which in turn are strongly dependent on interactions between solute advection (controlled by fluid flow rates), solute diffusion/dispersion and chemical kinetics. These interactions can be understood by simultaneously considering two dimensionless numbers, the Damköhler number and the Z -number. The Damköhler number expresses the interaction between solute advection (flow rate) and chemical kinetics, while the Z -number expresses the interaction between solute diffusion/dispersion and chemical kinetics. Based on the Damköhler and Z -numbers, two chemical equilibrium length-scales are defined, dominated by either solute advection or by solute diffusion/dispersion. For a permeable vertical fault zone and for a given solute diffusion/dispersion coefficient, there exist three possible types of chemical reaction patterns, depending on both the flow rate and the chemical reaction rate. These three types are: (i) those dominated by solute diffusion and dispersion resulting in precipitation at the lower tip of a vertical fault and as a thin sliver within the fault, (ii) those dominated by solute advection resulting in precipitation at or above the upper tip of the fault, and (iii) those in which advection and diffusion/dispersion play similar roles resulting in wide mineralization within the fault. Theoretical analysis indicates that there exists both an optimal flow rate and an optimal chemical reaction rate, such that chemical equilibrium following focusing and mixing of two fluids may be attained within the fault zone (i.e. type 3). However, for rapid and parallel flows, such as those resulting from a lithostatic pressure gradient, it is difficult for a chemical reaction to reach equilibrium within the fault zone, if the two fluids are not well mixed before entering the fault zone. Numerical examples are given to illustrate the three possible types of chemical reaction patterns. [source] Ab initio chemical kinetics for the NH2 + HNOx reactions, part II: Kinetics and mechanism for NH2 + HONOINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 11 2009Shucheng Xu The kinetics and mechanism for the reaction of NH2 with HONO have been investigated by ab initio calculations with rate constant prediction. The potential energy surface of this reaction has been computed by single-point calculations at the CCSD(T)/6-311+G(3df, 2p) level based on geometries optimized at the CCSD/6-311++G(d, p) level. The reaction producing the primary products, NH3 + NO2, takes place via precomplexes, H2N,,,c -HONO or H2N,,,t -HONO with binding energies, 5.0 or 5.9 kcal/mol, respectively. The rate constants for the major reaction channels in the temperature range of 300,3000 K are predicted by variational transition state theory or Rice,Ramsperger,Kassel,Marcus theory depending on the mechanism involved. The total rate constant can be represented by ktotal = 1.69 × 10,20 × T2.34 exp(1612/T) cm3 molecule,1 s,1 at T = 300,650 K and 8.04 × 10,22 × T3.36 exp(2303/T) cm3 molecule,1 s,1 at T = 650,3000 K. The branching ratios of the major channels are predicted: k1 + k3 producing NH3 + NO2 accounts for 1.00,0.98 in the temperature range 300,3000 K and k2 producing OH + H2NNO accounts for 0.02 at T > 2500 K. The predicted rate constant for the reverse reaction, NH3 + NO2 , NH2 + HONO represented by 8.00 × 10,26 × T4.25 exp(,11,560/T) cm3 molecule,1 s,1, is in good agreement with the experimental data. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 678,688, 2009 [source] A CFL-like constraint for the fast marching method in inhomogeneous chemical kineticsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2008Ramón Escobedo Abstract Level sets and fast marching methods are a widely used technique for problems with moving interfaces. Chemical kinetics has been recently added to this family, for the description of reaction paths and chemical waves in homogeneous media, in which the velocity of the interface is described by a given field. A more general framework must consider variable velocities due to inhomogeneities induced by chemical changes. In this case, a constraint must be satisfied for the correct use of fast marching method. We deduce an analytical expression of this constraint when the Godunov scheme is used to solve the Eikonal equation, and we present numerical simulations of a case which must be enforced to obey the constraint. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] The normal and cancerous living cellINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 14 2006Janos Ladik Abstract We do not have a definition of the living and cancerous states; we can give only their main characteristics at the different levels of organization: cell, organ, and organism. A simple model is proposed for a normal eukaryotic cell based on Prigogine's equation of chemical kinetics with diffusion. In this model, possibly only a few hundred key biochemical reactions should be selected together with their rate and diffusion constants. To solve these coupled nonlinear partial differential equation systems, it is proposed that the model cell be subdivided into compartments and that the problem be worked out always for one compartment (finite element method). This is possible, since the most important biochemical reactions and reaction cycles occur in different parts of the cell. The solutions (concentrations) obtained in one compartment can be used as input to the other compartments (together with the components entering from the environment). As an example, the problem of 10 reactions and 3 compartments has been solved by discretizing the space coordinates and choosing time steps. The solutions obtained by solving the 10 differential equations directly and by the compartmentalization agree very well. The main obstacles to further progress lie in the right choice of reactions and compartments, as well as in the correct estimation of the rate and diffusion constants, which were measured in only a few cases. If such a model cell can be obtained, the solutions should be investigated to determine (i) for their stability (homeostasis); (ii) whether changing the input concentrations to a larger degree one would obtain a new stationary state showing the characteristics of a precancerous state; and (iii) a method of extracting those input concentrations, or functions of them, which are the most important regulatory parameters. If successful, this would provide a scientific definition of the living state in the normal and cancerous states, respectively, at least at the cell level. Finally, outline is provided showing how the model might be extended to multicellular cases, as well as the main difficulties of such a process. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source] Symbolic methods for invariant manifolds in chemical kineticsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 1 2006Simon J. Fraser Abstract Chemical reactions show a separation of time scales in transient decay due to the stiffness of the ordinary differential equations (ODEs) that describe their evolution. This evolution can be represented as motion in the phase space spanned by the concentration variables of the chemical reaction. Transient decay corresponds to a collapse of the "compressible fluid" representing the continuum of possible dynamical states of the system. Collapse occurs sequentially through a hierarchy of nested, attracting, slow invariant manifolds (SIMs), i.e., sets that map into themselves under the action of the phase flow, eventually reaching the asymptotic attractor of the system. Using a symbolic manipulative language, explicit formulas for the SIMs can be found by iterating functional equations obtained from the system's ODEs. Iteration converges geometrically fast to a SIM at large concentrations and, if necessary, can be stabilized at small concentrations. Three different chemical models are examined in order to show how finding the SIM for a model depends on its underlying dynamics. For every model the iterative method provides a global SIM formula; however, formal series expansions for the SIM diverge in some models. Repelling SIMs can be also found by iterative methods because of the invariance of trajectory geometry under time reversal. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source] Rapid estimation of chemical kinetics by implicit calibration.JOURNAL OF CHEMOMETRICS, Issue 2 2003Abstract This study continues the development of a method, implicit calibration, for estimating kinetic parameters from on-line measurements of batch reactions. The basic idea of implicit calibration is to combine non-linear parameter estimation with the calibration of measured spectra with concentrations calculated by an assumed kinetic model. A new example is studied, an esterification reaction with a rather complicated kinetic mechanism, where activities, instead of concentrations, and NIR spectra are used as measurements. The emphasis in the study is on estimating the uncertainty of the kinetic parameters. Two approaches, linearization and bootstrap, are applied. In the case studied, the two approaches give closely similar estimates of the uncertainty. As well, a new way is introduced to control the rigidity of the implicit calibration, based on minimizing the lack of fit of the model. It is also shown that ,mixed implicit calibration', i.e. implicit calibration combined with a few off-line calibrated concentrations, greatly enhances the identifiability of the kinetic model. Copyright © 2003 John Wiley & Sons, Ltd. [source] A multi-objective optimization approach to polygeneration energy systems designAICHE JOURNAL, Issue 5 2010Pei Liu Abstract Polygeneration, typically involving co-production of methanol and electricity, is a promising energy conversion technology which provides opportunities for high energy utilization efficiency and low/zero emissions. The optimal design of such a complex, large-scale and highly nonlinear process system poses significant challenges. In this article, we present a multiobjective optimization model for the optimal design of a methanol/electricity polygeneration plant. Economic and environmental criteria are simultaneously optimized over a superstructure capturing a number of possible combinations of technologies and types of equipment. Aggregated models are considered, including a detailed methanol synthesis step with chemical kinetics and phase equilibrium considerations. The resulting model is formulated as a non-convex mixed-integer nonlinear programming problem. Global optimization and parallel computation techniques are employed to generate an optimal Pareto frontier. © 2009 American Institute of Chemical Engineers AIChE J, 2010 [source] The kinetics of the reduction of iron oxide by carbon monoxide mixed with carbon dioxideAICHE JOURNAL, Issue 4 2010C. D. Bohn Abstract Results are reported for the repeated reduction of iron oxide particles, 300,425 ,m diameter, by a mixture of CO, CO2, and N2 in a fluidized bed of 20 mm internal diameter. The conclusions were as follows: (1) Reduction of either Fe2O3 to Fe3O4 or of Fe3O4 to Fe0.947O is first-order in CO. (2) With the particle sizes used, the rates of the reduction reactions are controlled by intrinsic chemical kinetics. Activation energies and pre-exponential factors are reported. (3) The first cycle gave anomalous results, but (a) the rate of reduction of Fe2O3 to Fe3O4 remained constant over cycles 2,10; (b) the rate of reduction of Fe3O4 to Fe0.947O declined by 60,85% over cycles 2,10. (4) The rates of reduction declined with solids conversion down to zero at 80% conversion. The rates were incorporated into a conventional model of a fixed bed, which was used to predict, satisfactorily, the reduction behavior of iron oxide. © 2009 American Institute of Chemical Engineers AIChE J, 2010 [source] Effect of chemical kinetics on feasible splits for reactive distillationAICHE JOURNAL, Issue 3 2001Nitin Chadda Feasible direct and indirect sharp splits for multicomponent single-feed continuous reactive distillation are predicted with a model, in which each column section is represented by a series of cocurrent isobaric flashes. In the limits of no reaction and equilibrium chemical reaction, the model reduces to conventional models for distillation lines, and each column section can be represented by the same equations. At intermediate reaction rates, however, the models for the column sections differ, and new results for fixed points and feasible products are obtained. A bifurcation study shows the limits of feasibility, including the influence of flow rate, catalyst level and holdup. Unlike distillation without reaction, limited ranges of feasibility in all of these variables are found. The method has been applied to five examples, one of which is described in detail. Feasibility predictions are validated by column simulations. [source] A Determination of Hydration Mechanisms for Tricalcium Silicate Using a Kinetic Cellular Automaton ModelJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 7 2008Jeffrey W. Bullard Reaction mechanisms for the early stages of hydration of tricalcium silicate (Ca3SiO5) have not been agreed upon, although theories have appeared in the literature. In this paper, a mechanistic description is proposed that is consistent with a wide range of reported experimental observations, and which is supported quantitatively by simulations using HydratiCA, a new three-dimensional microstructure model of chemical kinetics. Rate processes are quantitatively modeled using probabilistic cellular automaton algorithms that are based on the principles of transition state theory. The model can test alternate assumptions about the reaction paths and rate-controlling steps, making it a kind of experimental tool for investigating kinetics and interpreting experimental observations. It is used here to show that hydration of Ca3SiO5 is most likely controlled by nucleation and growth of a compositionally variable calcium silicate hydrate solid, mediated at very early times by a transient, thermodynamically metastable solid that rapidly covers and sharply reduces the dissolution rate of Ca3SiO5. This proposed mechanism involves important elements of two leading theories of Ca3SiO5 hydration, neither of which alone has been able to capture the full range of experimental data when tested by the model. [source] Combined Effects of Hot Curing Conditions and Reaction Heat on Rubber Vulcanization Efficiency and Vulcanizate UniformityMACROMOLECULAR THEORY AND SIMULATIONS, Issue 4-5 2009Xiaoxia Wang Abstract A mathematical model of the chemical kinetics of silicone rubber vulcanization is developed, with the thermal effects being computed using the increment method, and the hot vulcanization process estimated with the finite element method. The results show that the reaction heat of rubber vulcanization is important for energy saving, and that a proper curing medium temperature is important when considering both vulcanization efficiency and vulcanizate uniformity. The results also indicate that increases in the forced convective heat transfer coefficient have no significant effect above a certain level. The validity of the numerical model is indirectly proven by comparison with existing data. [source] Amplitude,shape approximation as an extension of separation of variablesMATHEMATICAL METHODS IN THE APPLIED SCIENCES, Issue 3 2008N. Parumasur Abstract Separation of variables is a well-known technique for solving differential equations. However, it is seldom used in practical applications since it is impossible to carry out a separation of variables in most cases. In this paper, we propose the amplitude,shape approximation (ASA) which may be considered as an extension of the separation of variables method for ordinary differential equations. The main idea of the ASA is to write the solution as a product of an amplitude function and a shape function, both depending on time, and may be viewed as an incomplete separation of variables. In fact, it will be seen that such a separation exists naturally when the method of lines is used to solve certain classes of coupled partial differential equations. We derive new conditions which may be used to solve the shape equations directly and present a numerical algorithm for solving the resulting system of ordinary differential equations for the amplitude functions. Alternatively, we propose a numerical method, similar to the well-established exponential time differencing method, for solving the shape equations. We consider stability conditions for the specific case corresponding to the explicit Euler method. We also consider a generalization of the method for solving systems of coupled partial differential equations. Finally, we consider the simple reaction diffusion equation and a numerical example from chemical kinetics to demonstrate the effectiveness of the method. The ASA results in far superior numerical results when the relative errors are compared to the separation of variables method. Furthermore, the method leads to a reduction in CPU time as compared to using the Rosenbrock semi-implicit method for solving a stiff system of ordinary differential equations resulting from a method of lines solution of a coupled pair of partial differential equations. The present amplitude,shape method is a simplified version of previous ones due to the use of a linear approximation to the time dependence of the shape function. Copyright © 2007 John Wiley & Sons, Ltd. [source] ASYMPTOTIC METHODS: APPLICATION TO REDUCTION OF MODELSNATURAL RESOURCE MODELING, Issue 3 2000LEONID V. KALACHEV ABSTRACT. A survey of results on reduction of models related to problems of natural resource modeling using the boundary function method is presented. Detailed reduction procedures as well as conditions under which the reductions are at all possible are discussed. Particular asymptotic techniques are illustrated by simple examples taken from chemical kinetics, and a realistic example from atmospheric chemistry modeling. [source] Bayesian Calibration of a Stochastic Kinetic Computer Model Using Multiple Data SourcesBIOMETRICS, Issue 1 2010D. A. Henderson Summary In this article, we describe a Bayesian approach to the calibration of a stochastic computer model of chemical kinetics. As with many applications in the biological sciences, the data available to calibrate the model come from different sources. Furthermore, these data appear to provide somewhat conflicting information about the model parameters. We describe a modeling framework that allows us to synthesize this conflicting information and arrive at a consensus inference. In particular, we show how random effects can be incorporated into the model to account for between-individual heterogeneity that may be the source of the apparent conflict. [source] Evaluation of the Limiting Regime in Iron Ore Fines Reduction with H2 -Rich Gases in Fluidized Beds: Fe2O3 to Fe3O4CHEMICAL ENGINEERING & TECHNOLOGY (CET), Issue 3 2009J. Sturn Abstract In metallurgical processes, fluidized-bed technology is gaining more importance because of its advantages. Processes with H2 -rich and CO-rich reducing gases were developed for the reduction of iron ore fines (e.g. FINEX®). For improvement of these new technologies, greater knowledge about the chemical kinetics of iron ore reduction in fluidized beds is necessary. The scope of this work is to evaluate the limiting regime of the iron ore fines reduction. Therefore, experimental results of reduction tests were compared with theoretically investigated reduction rates. These reduction rates were based on a limitation either of mass transfer through the external gas film to the particle surface, diffusion in a porous product layer (pore diffusion and Knudsen diffusion), diffusion in a dense product layer (solid diffusion) or the phase boundary reaction. The phase boundary reaction was found to be the most likely limiting reaction regime. [source] Hydrogen Production from a Fluidized-bed Coal Gasifier with In Situ Fixation of CO2,Part I: Numerical ModelCHEMICAL ENGINEERING & TECHNOLOGY (CET), Issue 2 2008J. Lu Abstract In order to attempt to eliminate global warming effects, it is highly desirable that new technologies with lower or zero emission of CO2 to the environment are developed. In this work, a high-pressure fluidized-bed coal gasifier for H2 production with in situ fixation of CO2 is simulated by a comprehensive two-dimensional model. The Eddy Dissipation Concept (EDC) model is first adopted in the pulverized coal gasification model to simultaneously describe the turbulent mixing and detailed chemical kinetics. The developed model is verified with experimental results. The simulated concentrations for the gas product agree well with the experimental data. The simulated distributions for gas temperature and velocity correlate well with the reaction mechanism and experimental phenomena. [source] Simulating the Dynamics of Spouted-Bed Nuclear Fuel Coaters,CHEMICAL VAPOR DEPOSITION, Issue 9 2007S. Pannala Abstract We describe simulation studies of the dynamics of spouted beds used for CVD coating of nuclear fuel particles. Our principal modeling tool is the Multiphase Flow with Interphase eXchanges (MFIX) code that was originally developed by the National Energy Technology Laboratory (NETL) for fossil energy process applications. In addition to standard MFIX features that allow coupling of transient hydrodynamics, heat and mass transfer, and chemical kinetics, we employ special post-processing tools to track particle mixing and circulation as functions of operating conditions and bed design. We describe in detail one major feature of the dynamics, which is the occurrence of very regular spontaneous pulsations of gas and particle flow in the spout. These pulsations appear to be critically linked to the entrainment and circulation of solids, and they produce readily accessible dynamic pressure variations that can be used for direct comparisons of model predictions with experiments. Spouted-bed dynamics are important from a CVD perspective because they directly determine the magnitude and variability of the concentration and species gradients in the zone where reactant gases first come into contact with hot particles. As this unsteady spouted-bed environment differs from other types of CVD reactors, the design and scale-up of such reactors is likely to involve unique modeling issues. Our primary goal here is to lay the groundwork for how computational simulation can be used to address these modeling issues in the specific context of nuclear fuel particle coating. [source] Modellierung und Simulation von Chemiereaktoren , Aspekte einer zeitgemäßen IngenieurausbildungCHEMIE-INGENIEUR-TECHNIK (CIT), Issue 1-2 2005J. Hagen Prof. Abstract Die Durchführung chemischer Prozesse in der Technik unter möglichst optimalen Bedingungen setzt ein Grundverständnis für die Arbeitsweise von Chemiereaktoren voraus. Grundlage der Modellierung von Chemiereaktoren sind die Stoff- und Wärmebilanz und die Kinetik der Reaktion. Nur in einfachen Fällen lassen sich analytische Lösungen für Problemstellungen aus der Praxis durch Integration der Differentialgleichungen finden. Das in der Chemieingenieurausbildung eingesetzte Softwarepaket POLYMATH ist sehr anwenderfreundlich und einfach zu erlernen. Es wird u.,a. eingesetzt, um gekoppelte Differentialgleichungen simultan zu lösen und Datenanalyse durch Regression durchzuführen. Mit einem einmal aufgestellten Modell lässt sich der Einfluss verschiedener Reaktionsparameter auf den Gesamtprozess leicht nachvollziehbar simulieren. Modeling and Simulation of Chemical Reactors , Aspects of a Modern Education of Engineers Understanding how chemical reactors work lies at the heart of almost every chemical processing operation. Basis information for modeling and simulation of chemical reactors is needed from mass transfer, heat transfer and chemical kinetics. Only simple problems from practice can be solved analytically by means of integration of the differential equations. POLYMATH is a extremely user-friendly software package which makes modeling easy for the education of chemical engineers and chemists. POLYMATH is used to numerically solve coupled differential equations simultaneously or to find kinetic parameters in rate expressions by regression. Using an identified model the influence of various reaction parameters on the overall process can be simulated easily. [source] | ||||||||||||||||