chemkin3教程pdf.pdf

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UC-405 SAND96-8216 Unlimited Release Printed May 1996 CHEMKIN-III: A FORTRAN CHEMICAL KINETICS PACKAGE FOR THE ANALYSIS OF GAS- PHASE CHEMICAL AND PLASMA KINETICS Robert J. Kee, Fran M. Rupley, and Ellen Meeks Thermal and Plasma Processes Department and James A. Miller Combustion Chemistry Department Sandia National Laboratories Livermore, CA 94551-0969 ABSTRACT 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. 3

ACKNOWLEDGMENTS CHEMKIN-III now has the capability to handle weakly ionized plasma chemistry, especially for applications related to advanced semiconductor processing. This aspect of the work was supported, in large part, through a Cooperative Research and Development Agreement (CRADA) with SEMATECH. Dr. Andrew Labun, at Digital Equipment Corporation, has been very generous of his time and energies in suggesting the ways in which CHEMKIN can better meet the needs of the advanced semiconductor processing industry. Prof. Mark Cappelli at Stanford University provided an initial vision, which established the technical direction for the multi-fluid formulation that is implemented in CHEMKIN-III. CHEMKIN-III also has enhanced capabilities to handle a variety of pressure-dependent unimolecular-falloff and bimolecular chemically activated processes. Dr. Gregory Smith of SRI International and Dr. Jan Hessler of Argonne National Laboratory were instrumental in establishing the technical formulations and provided important suggestions on the software implementation. Finally, we are grateful to our many colleagues at Sandia and elsewhere, who have provided numerous suggestions and have patiently worked with us as applications have migrated from CHEMKIN-II to CHEMKIN-III. In particular, we acknowledge the efforts of Drs. Michael Coltrin, Gregory Evans, Joseph Grcar, Pauline Ho, William Houf, Richard Larson, Andrew Lutz, Chris Moen, Harry Moffat, and Jong Shon. 4

CONTENTS Page II. 6 LIST OF FIGURES........................................................................................................................... 6 LIST OF TABLES ............................................................................................................................ 7 NOMENCLATURE......................................................................................................................... 9 INTRODUCTION.................................................................................................................. I. 9 Background......................................................................................................................... 10 Structure and Use of CHEMKIN......................................................................................... 11 Example for a Single-Temperature Neutral Gas: Hydrogen Oxidation................................ 14 Example for a Multi-Temperature Plasma.......................................................................... Transportability............................................................................................................... 16 16 Organization of this Report............................................................................................... 18 THERMODYNAMICS AND CHEMICAL RATE EXPRESSIONS ........................................... Choice of Variables .......................................................................................................... 18 18 Equation of State and Conversion Formulas ........................................................................ 21 Standard-State Thermodynamic Properties....................................................................... 25 Chemical Reaction Rate Expressions.................................................................................. III. THE MECHANICS OF USING CHEMKIN........................................................................... 36 36 Structure of CHEMKIN ..................................................................................................... 38 Job Control ........................................................................................................................ IV. USING THE INTERPRETER................................................................................................. 39 39 Element Data.................................................................................................................... 42 Species Data..................................................................................................................... 43 Thermodynamic Data ....................................................................................................... Reaction Mechanism Description....................................................................................... 46 59 V. QUICK REFERENCE GUIDE TO THE GAS-PHASE SUBROUTINE LIBRARY ...................... Mnemonics ........................................................................................................................ 59 VI. ALPHABETICAL LISTING OF THE GAS-PHASE SUBROUTINE LIBRARY WITH VII. DETAILED DESCRIPTIONS OF THE CALL LISTS ............................................................... SAMPLE PROBLEM ........................................................................................................... 1. UNIX Shell Script for Running the Sample Problem .................................................... 2. Sample Input to the Interpreter.................................................................................... 3. Output from the Interpreter for the Sample Input.......................................................... 4. Sample User’s FORTRAN Code: CONP ....................................................................... 5. Input to the Sample FORTRAN Code, CONP............................................................... 6. Output form the Sample FORTRAN Code, CONP......................................................... 7. Summary of VODE Math Library Usage....................................................................... REFERENCES.............................................................................................................................. APPENDIX A. STORAGE ALLOCATION FOR THE WORK ARRAYS.......................................... 72 136 137 139 140 142 146 147 149 153 154 5

LIST OF FIGURES Figure 1. Figure 2. Figure 3. Figure 4. Figure 5. Figure 6. Sample neutral reaction mechanism as read by the CHEMKIN Interpreter. Sample plasma reaction mechanism as read by the CHEMKIN Interpreter. Rate constant as a function of pressure at fixed temperature for the unimolecular fall- off reaction CH3 + CH3 (+M) C2H6 (+M). The Troe and Lindemann forms are illustrated as are the low- and high-pressure limiting forms. Energy versus reaction coordinate diagram that illustrates the competition between a three-body recombination reaction, CH3 + CH3 (+M) C2H 6 (+M), and a chemically activated bimolecular reaction, CH3 + CH3 (+M) Rate constant as a function of pressure at fixed temperature for the chemically activated reaction CH3 + CH3 (+M) C2H5 + H (+M). The SRI and Lindemann forms are illustrated as are the low- and high-pressure limiting forms. Schematic diagram showing the structure of the CHEMKIN package and its relationship to an application code. C2H5 +H (+M). Figure 7. A sample UNIX command procedure showing the steps required to compile and run an application code using the CHEMKIN package. Equivalent ways to describe element information Equivalent ways to describe species information Figure 8. Figure 9. Figure 10. Examples of thermodynamic data input. Figure 11. Examples of reaction data Figure 12. Examples of auxiliary information definitions LIST OF TABLES Table I. Table II. Table III. Table IV. Table V. Summary of the Rules for Element Data Summary of the Rules for Species Data Summary of the Rules for Thermodynamic Data Summary of the Rules for Reaction Data Summary of the Rules for Auxiliary Information Data Page 12 15 31 31 32 37 38 40 42 45 49 54 Page 41 43 44 49 55 6

NOMENCLATURE CGS Units depends on n ergs / g ergs / g ergs / mole ergs / mole depends on reaction ergs / (g K) ergs / (g K) Coefficients of fits to thermodynamic data Standard state specific Helmholtz free energy of the kth species Mean specific Helmholtz free energy of a mixture Standard state molar Helmholtz free energy of the kth species Mean molar Helmholtz free energy of a mixture Pre-exponential factor in the rate constant of the ith reaction Specific heat capacity at constant pressure of the kth species Mean specific heat capacity at constant pressure Standard state molar heat capacity at constant pressure of the kth species ergs / (mole K) Molar heat capacity at constant pressure of the kth species ergs / (mole K) ergs / (mole K) Mean molar heat capacity at constant pressure ergs / (g K) Specific heat capacity at constant volume of the kth species ergs / (g K) Mean specific heat capacity at constant volume Molar heat capacity at constant volume of the kth species ergs / (mole K) ergs / (mole K) Mean molar heat capacity at constant volume moles / (cm3 sec) Chemical creation rate of the kth species moles / (cm3 sec) Chemical destruction rate of the kth species [cal / mole]* Activation energy in the rate constant of the ith reaction ergs / g Standard state specific Gibbs free energy for the kth species Mean specific Gibbs free energy of a mixture ergs / g ergs / mole Standard state molar Gibbs free energy for the kth species ergs / mole Mean molar Gibbs free energy of a mixture Specific enthalpy of the kth species ergs / g Mean specific enthalpy of a mixture ergs / g ergs / mole Standard state molar enthalpy of the kth species Molar enthalpy of the kth species ergs / mole Mean molar enthalpy of a mixture ergs / mole Reaction index Total number of reactions Species index Forward rate constant of the ith reaction Reverse rate constant of the ith reaction Total number of species Equilibrium constant in concentration units for the ith reaction Equilibrium constant in pressure units for the ith reaction Total molar concentration of a mixture depends on reaction depends on reaction depends on reaction depends on reaction moles / cm3 ank o an a o Ak A Ai cpk cp o Cpk Cpk Cp cvk cv Cvk Cv ˙Ck ˙Dk Ei o gk g o Gk G hk h o Hk Hk H i I k k fi kri K Kci K pi M[ ] * By default, Chemkin uses activation energies in calories instead of ergs. 7

o Number of coefficients in polynomial fits to C Rp Pressure Pressure of one standard atmosphere Rate of progress of the ith reaction Universal gas constant Universal gas constant, in same units as activation energy Standard state specific entropy of the kth species Mean specific entropy of a mixture Standard state molar entropy of the kth species Molar entropy of the kth species Mean molar entropy of a mixture Temperature Specific internal energy of the kth species Mean specific internal energy of a mixture Molar internal energy of the kth species Mean molar internal energy of a mixture Mass fraction of the kth species Mole fraction of the kth species ] Molar concentration of the kth species Molecular weight of the kth species Mean molecular weight of a mixture N P Patm qi R Rc o sk s o Sk Sk S T uk u Uk U Yk Xk [ Xk Wk W GREEK a ki b i r t k u ki ¢u ki ¢u ki ˙w k CGS Units dynes / cm2 dynes / cm2 moles / (cm3 sec) ergs / (mole K) [cal / (mole K)] ergs / (g K) ergs / (g K) ergs / (mole K) ergs / (mole K) ergs / (mole K) K ergs / g ergs / g ergs / mole ergs / mole moles / cm3 g / mole g / mole g / cm3 sec Enhanced third-body efficiency of the kth species in the ith reaction Temperature exponent in the rate constant of the ith reaction Mass density Characteristic chemical destruction time of the kth species Stoichiometric coefficient of the kth species in the ith reaction, u u = ¢ u ki ki ki Stoichiometric coefficient of the kth reactant species in the ith reaction Stoichiometric coefficient of the kth product species in the ith reaction Chemical production rate of the kth species mole / (cm3 sec) 8 - ¢ ¢ ¢

CHEMKIN-III: A FORTRAN CHEMICAL KINETICS PACKAGE FOR THE ANALYSIS OF GAS- PHASE CHEMICAL AND PLASMA KINETICS† I. INTRODUCTION The CHEMKIN package is one of three basic elements in a large and growing body of software designed to facilitate simulations of elementary chemical reactions in flowing systems. The other major elements are the transport property package1 and the surface chemistry package, Surface CHEMKIN-III.2, 3 These packages should not be considered “programs” in the ordinary sense. That is, they are not designed to accept input, solve a particular problem, and report the answer. Instead, they are software tools intended to help a user work efficiently with large systems of chemical reactions and develop FORTRAN representations of systems of equations that define a particular problem. It is up to the user to solve the problem and interpret the answer. A general discussion of this structured approach for simulating chemically reacting flow can be found in Kee and Miller.4 An important advantage of the general-purpose and problem-independent structure of CHEMKIN is that it allows the analyst to work with the same chemical input regardless of the particular problem. Thus there is no need to remember a different input protocol for different problems, and consequently, the time required to switch between problems or to develop a new application is minimized. Additionally, by making CHEMKIN easily transportable between computers, we hope to facilitate the exchange of application codes and data between different sites. Often such exchanges are hampered by machine-dependent or problem-specific coding. Background CHEMKIN-III is a revised, generalized version of CHEMKIN. The original CHEMKIN5 was published in 1980. CHEMKIN II6 expanded these capabilities, with inclusion of an accurate and efficient means of describing pressure-dependent reactions. The rate laws for reactions of this type do not follow the modified Arrhenius form that was required in the original CHEMKIN. Other added capabilities in CHEMKIN II included a Landau-Teller form of the rate expression for vibrational energy transfer processes, a capability for specifying more than one rate expression for a reaction, and a capability for explicitly specifying an Arrhenius expression for the reverse rate of a reversible reaction. The current extension of CHEMKIN allows for treatment of non-equilibrium multi-fluid systems. Multi-fluid systems are systems in which the momentum or energy for one or more species in a gas mixture differs significantly from that of the bulk mixture. In a plasma system, for example, ions and † Copyright © 1996, Sandia Corporation. The U. S. Government retains a nonexclusive license in this software as prescribed in AL 88-1 and AL 91-7. Export of this program may require a license from the United States Government. 9

electrons may be subject to electric fields that do not affect the neutral species transport. To track the motion of these species, a separate momentum equation must be solved that includes the force exerted by the electric field on the charged species. Similarly, electrons are subject to Joule-heating as they move along applied electric fields, requiring solution of a separate electron energy equation. Species momentum and energy equations can be derived as second and third moments about the Boltzmann equation, just as the species conservation equation results from the first moment of the Boltzmann equation. When all species are in thermal equilibrium and none are subject to special external forces, these equations can be summed over all species in the gas mixture to give the traditional equations of motion for a thermal system. In the CHEMKIN-III formulations, we allow for different species temperatures to control reaction dynamics and to determine species thermodynamic properties. For systems that are in thermal equilibrium, however, these relations collapse back to the original CHEMKIN formulations and should have no consequence to the CHEMKIN user. In addition to the multi-fluid generalization, new capabilities have been added for the inclusion of global reaction kinetics, with the option of user-specified reaction orders and the allowance of non-integer stoichiometric coefficients. This capability is useful both for plasma systems and also for describing thermal systems where information about detailed kinetics is not well known. The application of CHEMKIN to non-equilibrium plasma systems still requires, at this point, that the kinetics coefficients can be specified independent of the problem or application. For example, some assumption must be made a priori about the electron-energy distribution function (EEDF) when specifying electron-impact kinetics. In reality the EEDF will depend on the reactor conditions, such as the local electric field magnitude or the degree of dissociation of a molecular gas. These conditions are problem-dependent, such that including these effects requires close coupling between the kinetics-rate determination and the EEDF determination. While we foresee a need in future CHEMKIN development for treatment of fundamental reaction cross-section data, we believe there is still fairly wide opportunity for the application of problem-independent kinetics in plasma modeling. Such applications include plasma conditions where the EEDF is nearly Maxwellian, such as near-thermal atmospheric-pressure plasma jets, or very low-pressure, high-electron-density systems for microelectronics processing. New capabilities in this version of CHEMKIN also include additional reaction-rate fit types for expanded user flexibility. These fits have been specifically implemented for the incorporation of electron-impact kinetics, which are occasionally difficult to fit with Arrhenius expressions. Structure and Use of CHEMKIN The CHEMKIN package is composed of two blocks of FORTRAN code and two files: - the Interpreter (code) - the Gas-Phase Subroutine Library (code) - the Thermodynamic Database (file) - the Linking File (file). 10

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