C - CFD For FLUENT Manual: Hemkin

RELEASE 20091
CHEMKIN-CFD for FLUENT Manual

Simulating chemically reacting flows with detailed chemistry
CHEMKIN-CFD for FLUENT Module

CFD-FLU-20091-0905-UG-1 May 2009
Licensing:
For licensing information, please contact Reaction Design at (858) 550-1920 (USA) or licensing@ReactionDesign.com.
Technical Support:
Reaction Design provides an allotment of technical support to its Licensees free of charge. To request technical support, please include your license number along with input or output files, and any error messages pertaining to your question or problem. Requests may be directed in the following manner: E-mail: support@ReactionDesign.com, Fax: (858) 550-1925, Phone: (858) 550-1920. Additional technical support hours may also be purchased. Please contact Reaction Design for the hourly rates.
Copyright:
Copyright 2009 Reaction Design. All rights reserved. No part of this book may be reproduced in any form or by any means without express written permission from Reaction Design.
Trademark:
CHEMKIN and REACTION DESIGN are registered trademarks of Reaction Design in the United States and other countries. AURORA, CHEMKIN-CFD, CHEMKIN-MFC, CHEMKIN-CFD for FLUENT Module, CHEMKIN-PRO, CONP, CRESLAF, ENERGICO, EQUIL, EQUILIB, KINetics, MODEL FUELS CONSORTIUM, OPPDIF, OVEND, PARAMETER STUDY FACILITY, PARTICLE TRACKING FEATURE, PASR, PLUG, PREMIX, SENKIN, SHOCK, SPIN, SURFACE CHEMKIN, SURFTHERM, TRANSPORT, TWAFER, TWOPNT are all trademarks of Reaction Design or Sandia National Laboratories. ANSYS, CFX, and FLUENT are Trademarks or registered Trademarks of ANSYS Inc. and its subsidiaries located in the United States or other countries. All other trademarks are the property of their respective holders.
Limitation of Warranty:
The software is provided as is by Reaction Design, without warranty of any kind including, without limitation, any warranty against infringement of third party property rights, fitness or merchantability, or fitness for a particular purpose, even if Reaction Design has been informed of such purpose. Furthermore, Reaction Design does not warrant, guarantee, or make any representations regarding the use or the results of the use, of the software or documentation in terms of correctness, accuracy, reliability or otherwise. No agent of Reaction Design is authorized to alter or exceed the warranty obligations of Reaction Design as set forth herein. Any liability of Reaction Design, its officers, agents or employees with respect to the software or the performance thereof under any warranty, contract, negligence, strict liability, vicarious liability or other theory will be limited exclusively to product replacement or, if replacement is inadequate as a remedy or in Reaction Designs opinion impractical, to a credit of amounts paid to Reaction Design for the license of the software.
Acknowledgments:
This document contains excerpts from the manuals of the CHEMKIN software: CHEMKIN-CFD for FLUENT Module 20091 should be cited as: CHEMKIN-CFD for FLUENT Module 20091, Reaction Design: San Diego, 2009.
CHEMKIN-CFD for FLUENT
Contents
Table of Contents
1 Introduction..................................................................................................................................................................9
1.1 Information Resources ................................................................................................................................10 1.1.1 Contents of this Manual .............................................................................................................10 1.1.2 Installation and Licensing Manual ............................................................................................11 1.1.3 Tutorials .......................................................................................................................................11
Getting Started with CHEMKIN-CFD ....................................................................................................................13

2.1 2.2 2.3 2.4 Enabling the CHEMKIN-CFD Module in FLUENT ..................................................................................14 Setting Initial Conditions for Combustion Problems ...............................................................................17 Turbulence-Chemistry Interactions Models and CHEMKIN-CFD ........................................................17 Controlling Parameters in the FLUENT Text User Interface ................................................................18 2.4.1 Advanced Parameters Used in Steady-state Solution Algorithm .......................................23 2.4.2 Setting Up Monitor Cells for CHEMKIN-CFD .........................................................................24 User Programming.......................................................................................................................................25 Diagnostic Files and Error Messages .......................................................................................................25 2.6.1 Error Messages Printed in the FLUENT Graphical User Interface .....................................27 2.6.2 Diagnostic Messages in the KINetics-log.txt File ..................................................................30
2.5 2.6
Chemical Reaction Mechanisms...........................................................................................................................33

3.1 Provided, FLUENT-compatible Mechanisms ..........................................................................................33 3.1.1 Methane and Ethane Combustion Mechanism......................................................................34 3.1.2 Propane Combustion Mechanism ............................................................................................34 3.1.3 Hydrogen Combustion Mechanism .........................................................................................34 Locating Other Chemical Reaction Mechanisms....................................................................................35
3.2
Background Details for Working with Reaction Mechanisms .......................................................................37

A.1 A.2 Thermodynamic Property Database .........................................................................................................37 Gas-phase Kinetics Input ...........................................................................................................................41 A.2.1 Element Data...............................................................................................................................41 A.2.2 Species Data ...............................................................................................................................43 A.2.3 Thermodynamic Data (Optional) ..............................................................................................45 A.2.4 Reaction Data .............................................................................................................................46 A.2.5 Error Checks ...............................................................................................................................56 Surface Kinetics Input .................................................................................................................................57 A.3.1 Material Declaration ...................................................................................................................58 A.3.2 Site Data ......................................................................................................................................58 A.3.3 Bulk Data .....................................................................................................................................60
A.3
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Table of Contents
A.4
A.3.4 Thermodynamic Data.................................................................................................................62 A.3.5 Surface Reaction Mechanism Description .............................................................................63 A.3.6 Error Checks ...............................................................................................................................73 A.3.7 Mechanisms with Multiple Materials ........................................................................................75 TRANSPORT Input ..........................................................................................................................................76
Theoretical Background .........................................................................................................................................79

B.1 Gas-phase Reaction Rate Formulations ..................................................................................................79 B.1.1 Arbitrary Reaction Order ...........................................................................................................81 B.1.2 Three-Body Reactions ...............................................................................................................82 B.1.3 Pressure-Dependent Reactions ...............................................................................................83 B.1.4 Landau-Teller Formulation of the Rate Expressions ............................................................90 Surface Reaction Rate Formulations ........................................................................................................90 B.2.1 Development of a Surface Formalism .....................................................................................91 B.2.2 Surface Reaction Expressions and Equations.......................................................................96 B.2.3 Concentration Units ....................................................................................................................96 B.2.4 Surface Reaction Rate Expressions ........................................................................................97
B.2
Nomenclature ..........................................................................................................................................................111
C.1 C.2 C.3 Latin Equation Symbols ............................................................................................................................111 Greek Equation Symbols ..........................................................................................................................116 Subscript Equation Symbols ....................................................................................................................118
Index ..........................................................................................................................................................................121
2009 Reaction Design
CFD-FLU-20091-0905-UG-1
Contents
List of Tables
2-1 2-2 2-3 2-4 2-5 A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 Summary of Basic CHEMKIN-CFD Parameters ..............................................................................................................20 Summary of Advanced CHEMKIN-CFD Parameters .......................................................................................................21 Diagnostic Output Files Created During a CHEMKIN-CFD Run ......................................................................................26 Error Messages that May Be Printed to the FLUENT GUI ............................................................................................28 Other (non-License) Error Messages in KINetics-log.txt ...............................................................................................31 Summary of the Rules for Thermodynamic Data ..........................................................................................................39 Summary of the Rules for Element Data .......................................................................................................................43 Summary of the Rules for Species Data .......................................................................................................................44 Reaction Data Criteria ...................................................................................................................................................47 Summary of the Rules for Gas-phase Reaction Data ...................................................................................................49 Summary of the Rules for Gas-phase Auxiliary Information Data .................................................................................55 Error Checks .................................................................................................................................................................56 Summary of the Rules for Site Data ..............................................................................................................................60 Summary of the Rules for Bulk Data .............................................................................................................................61
A-10 Surface Reaction Data Criteria......................................................................................................................................65 A-11 Summary of the Rules for Surface Reaction Data ........................................................................................................66 A-12 Summary of the Rules for Surface Auxiliary Data .........................................................................................................71 A-13 Error Checks .................................................................................................................................................................73 A-14 Example Entries in a Transport Data file .......................................................................................................................77 C-1 C-2 Latin Symbols ..............................................................................................................................................................111 Greek Symbols ............................................................................................................................................................116
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List of Tables
C-3
Subscript Symbols.......................................................................................................................................................118
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Contents
List of Figures
2-1 2-2 2-3 2-4 A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 FLUENT Graphical User Interface ................................................................................................................................14 FLUENT Species Model Panel......................................................................................................................................15 FLUENT Import Chemkin Panel ....................................................................................................................................15 Text User Interface Commands for Changing CHEMKIN-CFD Parameters ....................................................................19 Excerpts from the Chemkin therm.dat Thermodynamic Database File .........................................................................39 Equivalent Ways to Describe Element Information .......................................................................................................43 Equivalent Ways to Describe Species Information........................................................................................................44 Examples of Reaction Data. ..........................................................................................................................................48 Examples of Gas-phase Auxiliary Information Data ......................................................................................................54 Examples of Site Data ...................................................................................................................................................59 Examples of Bulk Data ..................................................................................................................................................62 Examples of Surface Reaction Data .............................................................................................................................66 Examples of Auxiliary Surface Reaction Data ...............................................................................................................72
A-10 Surface Kinetics Input File using Multiple Materials ......................................................................................................75 B-1 B-2 B-3 B-4 B-5 B-6 B-7 Example Reaction for Adsorption, Using Atomic Site Formalism .................................................................................93 Example Reaction for Desorption, Using Atomic Site Formalism .................................................................................94 Example Reaction for Adsorption, Using Open Site Formalism ....................................................................................94 Illustration of an Adsorption Reaction using the Atomic Site Formalism .......................................................................95 Illustration of an Adsorption Reaction using the Open Site Formalism .........................................................................95 Examples of reactions with such non-integer coefficients ...........................................................................................100 Example of Sticking-coefficient Reaction with No Surface Species ............................................................................104
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List of Figures
B-8 B-9
Example of Sticking-coefficient Reaction with a Surface Site .....................................................................................104 Example of Sticking-coefficient Reaction with Multiple Surface Sites .........................................................................104
B-10 Langmuir-Hinshelwood Elementary Chemical Reactions ...........................................................................................106 B-11 Langmuir-Hinshelwood Single Overall Reaction .........................................................................................................107 B-12 Eley-Rideal Elementary Chemical Reaction................................................................................................................108 B-13 Eley-Rideal Single Overall Reaction ...........................................................................................................................108
CFD-FLU-20091-0905-UG-1
Introduction
Reacting flows are important to many industrial processes such as materials processing, engine design and chemical manufacturing. Many important design and process improvements require an understanding of the interplay between fluid transport, heat transfer and chemistry. The CHEMKIN-CFD for FLUENT Module incorporates CHEMKIN technology for formulating heterogeneous and gas-phase chemistry with an advanced solver approach designed specifically to work with the computational fluid dynamics (CFD) software, FLUENT. Reaction Design's CHEMKIN software is the market leader for micro-kinetic and detailed kinetics modeling of gas and gas-solid systems. Detailed models usually involve elementary reactions, where reactions paths represent molecular interactions and the breaking and forming of chemical bonds. Such chemical models provide accuracy and extensibility in predicting trace species emissions, critical chemical phenomena such as ignition or catalytic light-off, and materials deposition and chemical modification. CHEMKIN is used both to develop detailed mechanisms and to predict the performance of the chemistry in pre-defined flow conditions (e.g., well mixed regions, plug flows, channel flows, etc.). Reaction Design's CHEMKIN-CFD module provides an easy way to integrate the core capabilities of CHEMKIN into computational fluid dynamics (CFD) software for addressing reacting flows in arbitrary geometries. CHEMKIN and CHEMKIN-CFD are complementary products with applications in the chemical, automotive and semiconductor industries.
Throughout this manual, the symbol on the left will indicate notes that are particularly relevant to the CHEMKIN user or to CHEMKIN-CFD users who are already very familiar with CHEMKIN capabilities.
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Introduction
A common strategy for using CHEMKIN and CHEMKIN-CFD in modeling reacting flows includes some or all of the following: CHEMKIN Develop, test, and refine the chemical mechanism before including the additional complexity of multi-dimensional transport. Assist with systematic reduction of a chemical mechanism, if necessary, to develop a model within the computational constraints of the CFD model. Evaluate the impact of turbulent mixing on the chemistry in isolation from transport and diffusion. Create zonal or network models of gas turbines, IC engines, and reactor systems. CHEMKIN-CFD for FLUENT Module Dynamic or transient simulation of heat and mass transfer with chemical reactions in arbitrary geometries and transport environments. Steady-state simulation of heat and mass transfer with chemical reactions in arbitrary geometries and transport environments.
1.1
1.1.1
Information Resources
Reaction Design user documentation and tutorials are provided to assist you.
Contents of this Manual

This manual serves as a user guide for the fully coupled CHEMKIN-CFD for FLUENT package, where Reaction Designs CHEMKIN-CFD module has been closely integrated as a plug-in module to the FLUENT computational fluid dynamics package. To use CHEMKIN-CFD for FLUENT, users must describe their reaction mechanisms, thermodynamic data, and transport data in formats readable by the CHEMKIN or CHEMKIN-CFD software. This manual provides information needed to construct these input files.
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Introduction
The CHEMKIN input format has become a de facto standard for describing chemistry reaction mechanisms, which helps facilitate the exchange of data between different organizations. CHEMKIN-CFD for FLUENT is compatible with the latest version of CHEMKIN software, making it easy to use a hierarchical approach to modeling, where investigations transition from compact engineering models (for example, 0-D and 1-D approximations) to full 3-D complex-geometry design simulations. Chapter 2 provides step-by-step procedures for running a CHEMKIN-CFD for FLUENT problem within the FLUENT User Interface. Chapter 3 describes the FLUENTcompatible mechanisms that are provided as part of the CHEMKIN-CFD for FLUENT product. Appendix A provides guidance on creating and formatting the thermodynamic, gas-phase chemistry, surface chemistry, and transport input data, which may be needed in running a CHEMKIN-CFD for FLUENT problem. Finally Appendix B reviews the theoretical background behind the rate and property formulations, which may be helpful in generating new chemistry sets. Appendix C references the nomenclature used in the CHEMKIN formulations.
1.1.2
Installation and Licensing Manual

In addition to this manual, you may also wish to refer to the Installation and Licensing Manual, available from the Help menu after installation, or from the Reaction Design web site: http://poseidon/support/open/pub/license_utilities/Installation_and_Licensing. pdf
1.1.3
Tutorials
Tutorials for the CHEMKIN-CFD for FLUENT Module are available for download from the Reaction Design web site, including descriptive lessons and the associated tutorial data files. Go to http://www.reactiondesign.com/support/members/downloads_cfd/fluent/20091/ downloads_cfd_extras.shtml
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Introduction
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Getting Started with CHEMKIN-CFD

In this chapter, we describe the basic set-up procedure for a CHEMKIN-CFD for FLUENT problem, using the FLUENT user interface. Before getting started with CHEMKIN-CFD, however, it is important to verify that the FLUENT software and license is correctly installed, a license for CHEMKIN-CFD for FLUENT has been obtained, and that the reader has sufficient background on how to set up a new case in FLUENT. The pre-requisites for getting started with CHEMKIN-CFD for FLUENT then are: 1. FLUENT software (version 6.2 or higher) is installed on the users computer. 2. A FLUENT license file has been obtained from Ansys, Inc., and the appropriate license daemon has been successfully started to allow operation of FLUENT. 3. The user has successfully launched FLUENT, set up a new case (either a Fluent-supplied tutorial or a users own case), allowed the problem to iterate to a specified end time or steady-state, and verified the results through postprocessing. 4. A FLUENT_KINETICS license file has been obtained from Reaction Design or their agent for the computer where FLUENT is installed or for a license server that is networked to this computer.
To obtain a license for the CHEMKIN-CFD for FLUENT Module, please contact Sales@ReactionDesign.com.
5. The Reaction Design License Utilities have been installed and the License Server started, according to the instructions provided in the Installation and Licensing Manual.
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May 2009
Chapter 2: Getting Started with CHEMKIN-CFD
For help in installation of, licensing of, or training on FLUENT software, please contact an Ansys sales or support agent.
With this background established, the following sections discuss the details of enabling the CHEMKIN-CFD module within FLUENT, and setting controlling parameters for a chemically reacting flow problem.
2.1
Enabling the CHEMKIN-CFD Module in FLUENT

The CHEMKIN-CFD module is enabled through the FLUENT user interface. To begin, launch FLUENT in double-precision mode. The FLUENT User Interface should appear, as shown in Figure 2-1.
We recommend running the CHEMKIN-CFD module in Double Precision.
Figure 2-1
FLUENT Graphical User Interface
From the FLUENT User Interface menus, use the following steps to open an existing case, change the species calculation option to use CHEMKIN-CFD, and to set up the chemistry set to be employed: 1. Open an existing FLUENT case file from the File > Open menu. 2. Choose Define > Model > Species from the User Interface menu.
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3. From the Species Model panel, select KINetics by Reaction Design in the lower-left corner.
Figure 2-2 FLUENT Species Model Panel.
4. Click Apply. A panel will appear to allow importing of CHEMKIN chemistry files that are compatible with the CHEMKIN-CFD software, as shown in Figure 2-3.
Figure 2-3 FLUENT Import CHEMKIN Panel
Check the boxes to expand the panel and select surfacechemistry and transportproperty data files.
5.
Use this panel to browse to and select two or more CHEMKIN-formatted files for the data listed below. Use the check boxes at the bottom to enable selection of surface chemistry and gas-phase transport data files.
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a. Gas-phase thermodynamic data file, which includes thermodynamic data for all gas-phase species listed in the gas-phase chemistry file. This file is required. Details regarding the format of this file are included in Section A.1. b. Gas-phase chemistry file, including elements, species, and gas-phase reactions. This file is required. Details regarding the format of this file are included in Section A.2. c. Surface chemistry file, including surface site-phase definitions, site species, bulk (solid) species, and surface reactions. This file is only required if surface chemistry is included in the simulation. Details regarding the format of this file are included in Section A.3. d. Transport data file, which includes fundamental transport data for each of the gas-phase species listed in the gas-phase chemistry file. This file is required only if the molecular-theory transport option is selected in the FLUENT Species panel. Details regarding the format of this file are included in Section A.4.
In Appendix A we provide notes that may be of particular interest to CHEMKIN users, using the icon indicated here. These are intended to provide CHEMKIN users with quick reference information regarding how the implementation and input requirements in CHEMKIN-CFD may differ from that in CHEMKIN.
6. Once the chemistry-file selections are made, click OK. The CHEMKIN-based material will now be the default fluid definition in the Species Model panel. 7. Select the appropriate transport options for the case to be run. If a CHEMKIN transport data file was provided during the CHEMKIN Mechanism import, then the default option will be mixture-averaged for molecular diffusion, thermal conductivity, and viscosity. Other options may be selected by clicking on the Edit... button next to the Mixture Material selection.
The Full Multicomponent Diffusion option also uses the CHEMKIN Transport data, but uses FLUENTs multicomponent transport formulation, rather than the native CHEMKIN form.
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Once the CHEMKIN-CFD module is selected and the chemistry set has been processed successfully, the cell data can be initialized and iterations can begin as usual with FLUENT simulations. However, in some cases the user may need to modify default settings for the CHEMKIN-CFD module for optimal performance of the CHEMKIN-CFD solver. Refer to Section 2.4 for more information on CHEMKIN-CFD parameter settings.
2.2
Setting Initial Conditions for Combustion Problems

For combustion problems, particularly for steady-state simulations, it is important to choose the initial conditions carefully. Transient cases where auto-ignition is expected can be modeled directly using physical boundary and initial conditions that represent the actual experimental conditions. However other cases require some initial condition that will assure ignition. For example, if there is an external ignition source, such as a spark, pilot light, or match that is not included in the physical simulation, then it is important to introduce an initially elevated temperature sufficient to serve the purpose of ignition. This ensures that the numerical solution will be that of a burning gas, rather than that of a cold, unburned gas. The appropriate initial temperature will depend on the fuel and equivalence ratio, but typically a value of 1000-1600 K is sufficient. Such an elevated initial temperature can be applied to the entire fluid domain or to a local patch, depending on the nature of the problem and the expected flame location and the extent of the burning front.
2.3
Turbulence-Chemistry Interactions Models and CHEMKINCFD

FLUENT has several Turbulence-Chemistry Interactions Model options that can be selected in the Species Transport Model Panel. It is important to note here that only the Laminar Finite-Rate option will take full advantage of the CHEMKIN-CFD solver. Other options may use the CHEMKIN-CFD module routines to determine net species rates of production under conditions specified by the FLUENT solver, but will not benefit from any of the solver options described in Section 2.4. For non-Laminar kinetics, the CHEMKIN-CFD module assures consistency between CHEMKIN reaction mechanisms and the calculation of species production rates based on those mechanisms, but does not actually contribute to the solver methodology.
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2.4
Controlling Parameters in the FLUENT Text User Interface

The user has access to many parameter settings that can be used to control or improve the performance and convergence behavior of the CHEMKIN-CFD module. These parameters are accessed through FLUENTs Text User Interface (TUI), through typed text commands. In this section we describe the available parameters, their default values, and their recommended use. In general, default settings for the CHEMKIN-CFD parameters should be sufficient for most problems. However, it may be necessary to change these settings to improve performance for specific types of problems. In particular, the most appropriate solver parameters may vary depending on the nature of the chemistry set. For example, for chemistries with many trace species that have a large impact on solution results (i.e., the chemistry is stiff), solution tolerances should be relatively small (e.g., 1.E-9 to 1.E-12 for absolute tolerances and 1.E-4 to 1.E-5 for relative tolerances). For chemistry descriptions where all of the species included are within a few orders of magnitude in terms of mass fraction, however, much looser tolerances are more appropriate. Also, depending on the characteristic time scales of the dominant chemical reactions, the user may need to adjust the maximum time-step used by the CHEMKIN-CFD solver. Figure 2-4 shows an example series of TUI commands that change the tolerance values from their default settings. These parameter settings are stored in the case data files when the FLUENT case and data are saved. For more information about the general syntax and usage of the TUI in FLUENT, consult the FLUENT User Documentation.
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Figure 2-4
Text User Interface Commands for Changing CHEMKIN-CFD Parameters
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Table 2-1 and Table 2-2 summarize basic and advanced parameters, respectively. These tables include descriptions of the default values and physical units, where applicable, for each of the CHEMKIN-CFD parameters, as well as a discussion of the recommended parameter usage.
Table 2-1 Summary of Basic CHEMKIN-CFD Parameters
Parameter
Print Level
Usage
Controls the level of diagnostic printing to the CHEMKIN-CFD diagnostic output file, where 0 indicates no printing, 1 indicates standard printing, and 2 enables a verbose level of printing that provides details about the solver operations. Note that diagnostic output can significantly contribute to compute time such that high levels of printing should be avoided unless problems are encountered that require diagnosis.
Default Value
1
Absolute Tolerance for Gas-phase Species
Controls the smallest value of a species mass fraction that will be tracked by the CHEMKIN-CFD solver convergence algorithm. This should represent either the smallest mass fraction that is of importance in the problem or, for stiff chemistry, the smallest fraction pertaining to a species that can have a significant effect through chemical reaction on other species of interest. Typical values range from 1.E-6 to 1.E-12.
1.E-8
Relative Tolerance for Gas-phase Species
Controls the accuracy to which gas species mass fractions are resolved. Roughly this parameter controls the number of significant digits in the solution. However, this parameter can also be important for convergence of problems with stiff chemistry, as it is important to sufficiently resolve species that have a major impact on trace species of interest. Typical values range from 1.E-3 to 1.E-5.
1.E-4
Absolute Tolerance for Surface Species
Controls the smallest value of a surface species site fraction that will be tracked by the CHEMKIN-CFD solver convergence algorithm. This should represent either the smallest mass fraction that is of importance in the problem or, for stiff chemistry, the smallest fraction pertaining to a species that can have a significant effect through chemical reaction on other species of interest. Typical values range from 1.E-6 to 1.E-15.
1.E-8
Relative Tolerance for Surface Species
Controls the accuracy to which surface species site fractions are resolved. Roughly this parameter controls the number of significant digits in the solution. However, this parameter can also be important for convergence of problems with stiff chemistry, as it is important to sufficiently resolve species that have a major impact on trace species of interest. Typical values range from 1.E-3 to 1.E-5.
1.E-4
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Table 2-2
Summary of Advanced CHEMKIN-CFD Parameters
Parameter
Pseudo Timestepping Solver Option
Usage
Determines which solver to use during pseudo time-stepping used to improve the initial guess in a cell for steady-state simulations. By default, it is set to 1 and a robust solver with strict error control will be used when the steady-state algorithm requires time-stepping assistance. The user may optionally revert to a less accurate timestepping technique, which may be computationally faster but more prone to failure, by setting it to zero. See Section 2.4.1 for more information. This parameter is ignored for transient simulations.
Default Value
1
Pseudo Timestepping Size
This option is only relevant if the Pseudo Time-stepping Solver Option is set to 1 (the default setting). This controls the time interval for timestepping when time-stepping is used to assist a steady-state calculation. See Section 2.4.1 for more information. We recommend a value of 1.E-4 seconds for combustion problems.
1.E-6
[seconds]
Maximum Pseudo Time-stepping Attempts
This parameter controls how many iterations between time-stepping and steady-state solution attempts can be tried before the solver gives up and registers a failure for the cell. Usually only one attempt is needed, but the maximum can be increased from this default value in difficult cases. Note that in some cases it is most efficient to ignore a small number of cell failures early on in the simulation as long as these cells recover on subsequent iterations. See Section 2.4.1 for more information. We recommend a value of 10 to 100 to minimize error messages.
Maximum Time Step Allowed Minimum Time Step Allowed Initial Time Step for Solver
Maximum pseudo time-step value for time integration during steadystate solution. This value is relevant to steady-state simulations only.
1.E-2 [seconds]
Minimum pseudo time-step value for time integration during steadystate solution. This value is relevant to steady-state simulations only.
1.E-10
[seconds]
Initial time-step value for use in time integration. By default, the solver will automatically choose an appropriate initial time step, which is the recommended approach. In rare cases, however, control of initial time step value may improve convergence behavior. Upper Bound for Gas-species Mass Fraction Sets the upper bounds for the gas-phase species mass fractions during steady-state solution. In some cases, it may help convergence to allow species to go slightly over the physical bounds during interim steady-state iterations rather than forcing the bounds to be one. 0 (i.e., not specified)
[seconds]
1.01
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Table 2-2
Summary of Advanced CHEMKIN-CFD Parameters (Continued)
Parameter
Lower Bound for Gas-species Mass Fraction
Usage
Sets the lower bounds for the gas-phase species mass fractions during steady-state solution. In some cases, it may help convergence to allow species to go slightly negative during interim steady-state iterations rather than forcing the bounds to be zero. A value as negative as about -1.E-4 may be used.
Default Value
-1.E-12
Upper Bound for Surface Site Fraction
Sets the upper bounds for the surface species site fractions during steady-state solution. In some cases, it may help convergence to allow species to go slightly over the physical bounds during interim steadystate iterations rather than forcing the bounds to be one.
1.1
Lower Bound for Surface Site Fraction
Sets the lower bounds for the surface species site fractions during steady-state solution. In some cases, it may help convergence to allow species to go slightly negative during interim steady-state iterations rather than forcing the bounds to be zero.
-1.E-4
Small Positive Value to Replace Negative Species Fractions Enter Auxiliary Input File
This value will be used to substitute any non-positive species fractions during interim steady-state iterations. In some cases, setting this to a very small positive number may aid convergence for the steady-state solver. A filename in the local working directory containing auxiliary parameter information. This option does not have any use at this time, but may be used in future to enable access to user parameters that may be available in future interim updates by Reaction Design of the CHEMKINCFD module.
1.E-12
Enter Arbitrary String
Parameter string for indicating a parameter that has not yet been defined for the current FLUENT release. This option has no use at this time, but may allow access to new user parameters that may be introduced in future interim updates by Reaction Design of the CHEMKIN-CFD module.
Enter Arbitrary Value
Value associated with the parameter indicated by the Arbitrary String above. Again, this option has no use at this time, but may allow access to new user parameters that may be introduced in future interim updates by Reaction Design of the CHEMKIN-CFD module.
0 units depend on parameter string
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2.4.1
Advanced Parameters Used in Steady-state Solution Algorithm

Many of the parameters listed in Table 2-2 are relevant only for steady-state solution. Here we provide a brief description of the steady-state solution algorithm in order to clarify the role of these parameters and their impact on solution convergence. For steady-state problems, the CHEMKIN-CFD module is called by FLUENT for each cell during each FLUENT iteration towards a steady state. Within each cell, the CHEMKIN-CFD module will attempt to determine an appropriate steady-state using a combination of a modified Newton-iteration procedure and a pseudo time-stepping procedure. The Newton-iteration method is used to attempt to directly iterate towards the desired solution. However, at early times in the simulation, this procedure may not succeed, especially when the initial guess is far from the actual steady solution. In such cases, the CHEMKIN-CFD module will automatically switch to a time-stepping mode to advance the initial guess closer to the physical solution. After taking a certain number of time steps, the Newton-iteration algorithm tries again. In this way, the steady-state solution is achieved with a minimum amount of time-stepping. Since time-stepping is computationally expensive, this results in a computationally efficient but robust method for achieving the steady-state solution. The user can control the number of times the CHEMKIN-CFD module is allowed to use time-stepping to advance a solution towards steady-state before reporting a failure for any individual cell (see Maximum Pseudo Time-stepping Attempts in Table 2-2). In performing the pseudo time-stepping procedure, there are two solver options - a basic time-stepping procedure and a robust time-stepping procedure (see Pseudo Time-stepping Solver Option in Table 2-2). The robust procedure (default) uses an integration method that is very accurate with error control enforced on all solution variables. This can sometimes be more time consuming but is generally more reliable in tracking transient states towards an eventual steady condition. The basic solver option is much more approximate in the time-tracking technique, but is often faster and sufficiently robust for some cases. When the robust time-stepping procedure is selected, the user can specify the time interval used for each attempt to advance the solution using time integration (See Pseudo Time-stepping Size in Table 2-2). The actual time steps used during the time integration will be automatically determined based on the rate of change of the solution variables. The time interval, however, controls the total time advanced before returning the solution to be used as the next initial guess in the Newtoniteration.method.
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In addition to the pseudo time-stepping controls, the user may also control certain parameters that affect the convergence behavior of the Newton-iteration algorithm itself. In particular, the user can modify the solution bounds imposed during the iterations (see Upper Bounds and Lower Bounds parameters in Table 2-2). By extending the bounds slightly outside of the physical limits, the Newton iteration can more easily resolve species fractions that are very near to those limits. This can be especially helpful in early iterations where variable values may be changing rapidly. It is also helpful to try to reset any negative species fractions to very small values between iterations, so that these values do not have unphysical effects on reaction rates. For this purpose, the user can specify a small positive value, which should not exceed the specified absolute tolerance, as a replacement value for negative fractions (see Small Positive Value to Replace Negative Species Fractions in Table 2-2).
2.4.2
Setting Up Monitor Cells for CHEMKIN-CFD

At the same level of the basic-options and advanced-options in the Text User Interface, i.e., under define/models/species/KINetics-parameters, the user can add, delete, and list monitor cells. By specifying a monitor cell in the CHEMKIN-CFD options, the user is requesting additional printout diagnostics for every iteration or time-step at this cell location. Such printout can add significantly to computational times and should be avoided unless there is a problem has been encountered and more diagnosis is needed.
Using monitor cells may add significantly to the job run time. We recommend that monitor cells only be included if extra diagnosis is required to resolve a convergence problem or local mesh issue, for example.
Monitor cells are added using the add-cell-monitor option and providing the physical coordinates that correspond as closely as possible to the centroid location of the desired cell in the FLUENT mesh. More than one cell monitor can be created and they can all be deleted using the delete-cell-monitor option. The user may also list the currently activated monitor cells using the list-cell-monitor option.
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2.5
User Programming
For both gas-phase and surface kinetics reaction mechanisms, users have the option to provide custom reaction-rate formulations or to actually over-ride the entire set of species rates-of-production calculations with a user-provided subroutine. The gasphase options are described in more detail in Section A.2.4.1 and in Section A.2.4.3.10, while the surface options are described in more detail in Section A.3.5.1 and in Section A.3.5.3.9. Briefly, to turn on user-programmed rate routines, the user must include either USRPROG, or USRPROD auxiliary keywords in the gas-phase kinetics or surface kinetics input file. The USRPROG option is entered after a specific reaction line, and indicates that the rate-of-progress calculation for that particular reaction will be replaced by a user-routine call. The USRPROD option, however, is entered on the REACTION line and signals that a user routine will provide calculation of all species net production rates, regardless of the rest of the kinetics input in the file. For gas-phase chemistry, the applicable user routines for the USRPROG and USRPROD options are CKUPROG and CKUPROD, respectively. Templates for these subroutines are provide in the FORTRAN file cklib_user_routines.f. For surface chemistry, the applicable user routines for the USRPROG and USRPROD options are SKUPROG and SKUPROD, respectively. Templates of these subroutines are found in sklib_user_routines.f.
Please contact Reaction Design Support (support@reactiondesign.com) to obtain the userroutine templates as well as makefiles that allow compiling of the user-programmed functionality into the CHEMKIN-CFD module.
2.6
Diagnostic Files and Error Messages

In addition to the standard FLUENT files produced during a CHEMKIN-CFD for FLUENT run, the CHEMKIN-CFD module creates special files to hold diagnostic output and error messages that may be helpful in diagnosing a problem with the preprocessing or run steps. In addition, error messages may be written in the FLUENT Graphical User Interface window during run-time processing.
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Table 2-3 lists additional files that may be created by CHEMKIN-CFD, the data printed to them, and an indication of where they are created in the FLUENT run process. All files are created within the working directory of the simulation run. The actual names of many of the files will depend on variables, such as the chemistry-set file names, the case-file name, the cell number, iteration or time-step number, and the processor id. Such variables are indicated by < > in Table 2-3.
Table 2-3 Diagnostic Output Files Created During a CHEMKIN-CFD Run
Filename
<gas_chemistry>.out
When File Is Created

Always created during preprocessing, upon saving the CHEMKIN mechanism definition.
Contents Description
This file echoes back the gas-phase chemistry reaction set, species names, and elements in formatted text. In addition, detailed error messages are contained in this file in case an error is encountered while processing the gasphase chemistry input file and gas-phase thermodynamic data.
chem.asc
Always created during preprocessing, upon saving the CHEMKIN mechanism definition.
A Linking File used to transfer the preprocessed information to the CHEMKIN-CFD module at run-time. This file is typically not viewed by the user, but may occasionally be requested by Technical Support during problem diagnosis.
<surface_chemistry>.out
Created during preprocessing, only if surface chemistry box is checked in CHEMKIN mechanism definition.
This file echoes back the surface chemistry reaction set and the surface phase and species names. In addition, detailed error messages are contained in this file in case an error is encountered while processing the surface chemistry input file and surface-species thermodynamic data.
surf.asc
Created during preprocessing, only if surface chemistry box is checked in CHEMKIN mechanism definition.
<transport_data>.out
Created during preprocessing, only if transportproperty box is checked in CHEMKIN mechanism definition.
This file echoes back the transport-data fitting coefficients in formatted text. In addition, detailed error messages are contained in this file in case an error is encountered while processing the gasphase transport data.
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Table 2-3
Diagnostic Output Files Created During a CHEMKIN-CFD Run (Continued)
Filename
tran.asc
When File Is Created

Created during preprocessing, only if transportproperty box is checked in CHEMKIN mechanism definition.
Contents Description
KINetics-log.txt
Created when the simulation run is initiated.
Messages are written to this file that record the progress of chemistry-set pre-processor, license check-out, and CHEMKIN-CFD solver. The printing level during the simulation run can be controlled by Print Level as indicated in Table 2-1.
KINCELL_<cell_id>_ <iteration_number>.DBG
Created for Monitor Cells (see Section 2.4.2) at every iteration or time-step, any time that the Print Level (Table 2-1) is >0. Also created any time that a cell fails in the CHEMKIN-CFD solver and the Print Level is >0.
Includes debug information, including the actual input sent into the CHEMKIN-CFD module by FLUENT for the particular cell and iteration. This information may be requested by Reaction Design Technical Support when diagnosing cell failures.
2.6.1
Error Messages Printed in the FLUENT Graphical User Interface

Table 2-4 lists possible error messages that may appear in the FLUENT Graphical User Interface during a CHEMKIN-CFD for FLUENT run. The table includes recommended actions that may help resolve or narrow down the problem. In some cases, the user may be referred to some of the additional diagnostic output files generated by the CHEMKIN-CFD module and listed in Table 2-3.
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Table 2-4
Error Messages that May Be Printed to the FLUENT GUI
Error Message
Cannot read gas-phase chemistry input file.
Recommended Action
Verify the filename and file path for the gas-phase chemistry input file in the CHEMKIN Import panel and reimport.
Cannot read surface chemistry input file.
Verify the filename and file path for the surface chemistry input file in the CHEMKIN Import panel and re-import.
Cannot read thermodynamic data file.
Verify the filename and file path for the thermodynamic data file in the CHEMKIN Import panel and re-import.
Cannot read transport properties data file.
Verify the filename and file path for the transport-property data file in the CHEMKIN Import panel and re-import.
Cannot read gas-phase chemistry linking data file during gas-phase pre-processing. Cannot read gas-phase chemistry linking data file during surface pre-processing. Cannot read gas-phase chemistry linking data file during transport pre-processing. Cannot read surface chemistry linking data file during surface pre-processing. Cannot read transport properties linking data file during transport pre-processing. Cannot write gas-phase chemistry output file.
Check the <gas_chemistry>.out file in the working directory for error messages. Check the <gas_chemistry>.out file in the working directory for error messages. Check the <gas_chemistry>.out file in the working directory for error messages. Check the <surface_chemistry>.out file in the working directory for error messages. Check the <transport_data>.out file in the working directory for error messages. Check file permissions on working directory and make sure that there is only one CHEMKIN-CFD for FLUENT process using these files at a time.
Cannot write surface chemistry output file.
Check file permissions on working directory and make sure that there is only one CHEMKIN-CFD for FLUENT process using these files at a time.
Cannot write transport properties output file.
Check file permissions on working directory and make sure that there is only one FCHEMKIN-CFD for FLUENT process using these files at a time.
Cannot write gas-phase chemistry linking data file.
Cannot write surface chemistry linking data file.
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Table 2-4
Error Messages that May Be Printed to the FLUENT GUI (Continued)
Error Message
Cannot write transport properties linking data file.
Recommended Action
Gas-phase chemistry file is NULL.
Verify gas-phase chemistry file path in the CHEMKIN Mechanism definition and re-import the chemistry files.
Surface chemistry file is NULL.
Verify surface-chemistry file path in the CHEMKIN Mechanism definition and re-import the chemistry files.
Thermodynamic data file is NULL.
Verify thermodynamic-data file path in the CHEMKIN Mechanism definition and re-import the chemistry files.
Transport properties data file is NULL.
Verify transport-data file path in the CHEMKIN Mechanism definition and re-import the chemistry files.
Failure in pre-processing of gas-phase chemistry mechanism. Failure in pre-processing of surface chemistry mechanism. Failure in pre-processing of transport properties. Failure in CHEMKIN Gas-phase library call.
Check the <gas_chemistry>.out file in the working directory for error messages. Check the <surface_chemistry>.out file in the working directory for error messages. Check the <transport_data>.out file in the working directory for error messages. This is likely due to an overflow or invalid number being passed to the CHEMKIN-CFD module by FLUENT. Check to see if the FLUENT solution has diverged or has unphysical values for the variables. Try turning Print Level > 0 and setting a monitor cell to obtain more information.
Failure in CHEMKIN Surface library call.
This is likely due to an overflow or invalid number being passed to the CHEMKIN-CFD module by FLUENT. Check to see if the FLUENT solution has diverged or has unphysical values for the variables. Try turning Print Level > 0 and setting a monitor cell to obtain more information.
Failure in CHEMKIN Transport library call.
This is likely due to an overflow or invalid number being passed to the CHEMKIN-CFD module by FLUENT. Check to see if the FLUENT solution has diverged or has unphysical values for the variables. Try turning Print Level > 0 and setting a monitor cell to obtain more information.
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Table 2-4
Error Messages that May Be Printed to the FLUENT GUI (Continued)
Error Message
Need to run CHEMKIN-CFD PreProcess first.
Recommended Action
Re-import the CHEMKIN chemistry set and make sure it is selected in the Define=>Model=>Species panel.
No surface data for the chemistry set.
Either de-select the Surface Chemistry option in the CHEMKIN Import panel, or make sure that a valid surface chemistry file is indicated.
No transport data for the chemistry set.
Either de-select the Transport Data option in the CHEMKIN Import panel, or make sure that a valid transport data file is indicated.
Failure in writing data into the diagnostics file.
Check file permissions on the working directory and make sure that there is only one CHEMKIN-CFD for FLUENT process using these files at a time.
Error in CHEMKIN-CFD model, see diagnostic output file for details. License error in CHEMKIN-CFD model, see diagnostic output file for details.
Check the KINetics-log.txt file in the working directory for error messages. See Section 2.6.2 for more information. Check the KINetics-log.txt file in the working directory for the exact license-error message. See Section 2.6.2 for more information.
2.6.2
Diagnostic Messages in the KINetics-log.txt File

The KINetics-log.txt file is a catch-all for many diagnostic messages that are generated by the CHEMKIN-CFD module. The most common types of messages are license-error messages and cell-convergence error messages. License-error messages contain the text ERROR: could not get a license and Flexlm error report: , usually followed by an error-report string and error-report number. The error-report string usually provides a description of the license problem and the error-report number can be used to look up more information in the FlexLM end-user manual provided with the Reaction Design License Utility install.
To obtain help on licensing problems, please provide the complete license-error message found in the KINetics-log.txt file to support@reactiondesign.com.
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Cell-convergence error messages can take a variety of forms. The most common are summarized in Table 2-5. In general, if there are just a few failed cells at the beginning of a simulation it is safe to ignore them. When the number of failed cells continues to grow with each iteration, there is likely an issue with the problem set-up or with the chemistry data. Table 2-5 contains some broad suggestions of ways to improve cell-convergence behavior based on the type of cell failure message received.
Table 2-5 Other (non-License) Error Messages in KINetics-log.txt
Error Message
FAILURE INITIALIZING SETTINGS FOR THE KINetics STEADY-STATE GAS-PHASE CHEMISTRY SOLVER
Recommended Action
Most likely suggests an error in setting the convergence criteria (i.e. absolute and relative tolerance) and the pseudo-steady-state time stepping parameters. Check that the user-provided values are reasonable.
WARNING: Exceeded allowed time-stepping intervals in cell
Indicates that a convergence problem was encountered during steady-state solution, where timestepping is used to help advance the steady-state iterations. In this case, you can either ignore the message (see if the cell convergence recovers in subsequent iterations) or try to increase either the time interval or the number of allowed time-stepping intervals (See Table 2-2 for more information).
KINETICS ERROR: SOLUTION FAILED
Indicates that the cell failed to converge (either steadystate or transient).In this case, you can either ignore the message (see if the cell convergence recovers in subsequent iterations) or try to modify some of the user-controlled parameters to improve convergence (See Table 2-2 for more information).
Warning - The transient chemistry solver tried 500 steps without convergence in this cell; 500 more steps will be allowed
Indicates that the problem is difficult to converge so that the transient solver is taking extra steps. However, it is only a warning and the cell has not actually failed. If you receive an excessive number of these messages, try reducing the absolute or relative solution tolerances that control the CHEMKIN-CFD solver.
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Table 2-5
Other (non-License) Error Messages in KINetics-log.txt (Continued)
Error Message
KINETICS ERROR: Problem getting species names; Check that the CHEMKIN files have been processed correctly KINETICS ERROR: Problem getting surface chemistry info; Check that the CHEMKIN files have been processed correctly DASPK:...
Recommended Action
Indicates a possible error in the pre-processing of the gas-phase chemistry input file. Check the <gas_chemistry>.out file for error messages. Indicates a possible error in the pre-processing of the surface chemistry input file. Check the <surface_chemistry>.out file for error messages. These messages are from the CHEMKIN-CFD transient solver, DASPK. The exact message usually contains more information about the problem. You may also refer to the FAQ on transient convergence issues on Reaction Designs web site: http://www.reactiondesign.com/discus/messages/ 76/397.html
During steady-state simulations, once an iteration occurs where there are no failed cells, the effect of previously failed cells in earlier iterations is completely erased.
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Chemical Reaction Mechanisms

All CHEMKIN-CFD projects require input data provided by a chemical reaction mechanism (also called a chemistry set). The mechanism components are: A file containing thermochemical data for the chemical species of interest. A file containing a description of the reactions occurring in the gas phase. A file containing a description of the reactions occurring at the gas-surface interface or on the surface. (Optional) A file containing gas-phase transport data. (Optional) A set of gas-phase and/or surface reactions generally are developed using specific thermochemical data. Thus, the gas-phase kinetics, surface kinetics, and thermodynamic data are treated as a chemistry "set" in reacting-flow simulations. The install of CHEMKIN-CFD/FLUENT includes several fuel-combustion mechanisms that are appropriate for use in CHEMKIN-CFD for FLUENT. These are described in Section 3.1.
3.1
Provided, FLUENT-compatible Mechanisms

CHEMKIN-CFD for FLUENT provides reaction mechanisms, thermodynamic data and transport data for the following mechanisms that have been assembled specifically to have 50 or fewer species to accommodate the maximum species limit in FLUENT: a. Methane / Ethane: 50-species version of GRI-Mech 3.0 (grimech30_50spec). b. Propane: 37-species high-temperature mechanism (Propane-NOx_highT). c. Hydrogen: two mechanisms: 9-species version for H2 combustion (H2_mech). 21-species version for H2 combustion with NOx (H2_NOx_mech).
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May 2009
Chapter 3: Chemical Reaction Mechanisms
These mechanisms are described in the following sections, including references to source data and the recommended range of application.
3.1.1
Methane and Ethane Combustion Mechanism

The 50-species methane combustion mechanism (grimech30_50spec) is the original GRI-mech 3.01 (53 species) with three species and their reactions removed. The three removed species are AR, C3H8, and C3H7 (argon, propane, and propyl radical). It is expected that the removal of these species will have negligible effect on the mechanism's predictive capabilities for methane and ethane as fuels in fuel/air or fuel/oxygen combustion. The applicability of the GRI mechanism and validation cases are provided on the GRI mechanism web site1.
3.1.2
Propane Combustion Mechanism

The propane mechanism (Propane-NOx_highT) has 37 chemical species and 211 elementary reaction steps. It was obtained by removing species and reactions that are unimportant for propane combustion from the comprehensive master mechanism2. Reaction Workbench software3 was used to reduce the master mechanism under the conditions of slightly lean and high pressure laminar flame of a propane/air mixture using the Directed Relational Graph method.
3.1.3
Hydrogen Combustion Mechanism

The hydrogen combustion mechanism (H2_mech) contains 9 chemical species and 21 elementary reaction steps. This mechanism has been extracted from the Li et al.4 mechanism for CO and other hydrocarbons. The hydrogen combustion mechanism with NOx (H2_NOx_mech) contains 21 species and 105 elementary reaction steps. The hydrogen combustion submechanism is the same as the "H2_mech" mechanism, above. The NOx submechanism is based on the recent study by the Glarborg group5.
1. 2.
3. 4. 5.
Smith, G. P., D. M. Golden, et al. "GRI-Mech 3.0." 2008, from http://www.me.berkeley.edu/gri_mech/. Naik, C. V., K. V. Puduppakkam, et al. (2008). Modeling Combustion Characteristics of Components of Model-Biodiesel at High Temperatures. WSS/CI Spring 2008 Meeting, Los Angeles, CA. CHEMKIN-MFC 3.0, Reaction Design: San Diego, 2008. Li, J., Z. Zhao, et al. (2007). "A Comprehensive Kinetic Mechanism for CO, CH2O, and CH3OH Combustion." Int. J. Chem. Kinet. 39: 109-136. Rasmussen, C. L., A. E. Rasmussen, et al. (2008). "Sensitizing Effects of NOx on CH4 Oxidation at High Pressure." Comb. Flame 154(3): 529-545.
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Chemical Reaction Mechanisms
3.2
Locating Other Chemical Reaction Mechanisms

If a system of interest has been modeled by previous workers in the field, it may be possible to find a complete set of files that constitute a chemistry set, or published literature that provides a reaction mechanism. Reaction Design's web site includes a Chemical Mechanism Data page under Support. This page includes links to a number of web sites that contain posted reaction mechanisms and other chemical data. In addition, Reaction Design has extensive experience in assembling, testing, and reducing reaction mechanisms for a variety of applications. Please see the Reaction Design web site for more information about Reaction Design application services.
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Chapter 3: Chemical Reaction Mechanisms
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Background Details for Working with Reaction Mechanisms

This appendix provides guidance on creating and formatting the thermodynamic, gasphase chemistry, surface chemistry, and transport input data, which may be needed in running a FLUENT/CHEMKIN-CFD problem: Thermodynamic Property Database Gas-phase Kinetics Input Surface Kinetics Input Transport Input page 37 page 41 page 57 page 76
A.1
Thermodynamic Property Database

In setting up a new CHEMKIN mechanism in FLUENT/CHEMKIN-CFD, the user must specify thermodynamic and composition data for all of the species in the system, either by specifying a thermodynamic database file that contains all species, by including thermodynamic data in the reaction-mechanism input file(s), or by a combination thereof. The CHEMKIN standard thermodynamic database is a source for over 800 species and is available to CHEMKIN-CFD users. However, it may be necessary at times to either assemble a new thermodynamic database file or augment an existing one by adding thermodynamic data for certain species. This chapter describes the format of the thermodynamic data file and of the thermodynamic data when included within the gas-phase or surface chemistry mechanism files.
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Chapter A: Background Details for Working with Reaction Mecha-
The calculation of thermodynamic properties within FLUENT are performed separately from the calculations performed within CHEMKIN-CFD routines. For this reason, some CHEMKIN extensions are not available for the FLUENT/CHEMKIN-CFD package, although FLUENT uses the same basic format as CHEMKIN for thermodynamic property input. Extensions not available with FLUENT are the ability to: a) include more than two temperature regions in the polynomial fits, b) include more than 9 elements in a species composition, and c) allow more than 99 atoms of any element in a molecule.
The thermodynamic data file consists of polynomial coefficients for fits to temperature of specific heats, enthalpies and entropies for each species in the system. The thermodynamic data entries also contain the species' name, its elemental composition, its electronic charge, and an indication of its phase (gas, solid, liquid or solid). For each species, seven polynomial coefficients are needed for fits over each of two temperature ranges, as shown in Equation A-1 through Equation A-3. These fits take the following form, where the temperatures are in Kelvin:
Equation A-1
C pk ------- = a1 k + a2k Tk + a3 k Tk2 + a4 k Tk3 + a5 k Tk4 R

Equation A-2
Hk a2k a3k 2 a4k 3 a5k 4 a6k -------- = a 1 k + ------ T k + ------ T + ------ T + ------ T + -----RT k 2 3 k 4 k 5 k Tk
Equation A-3
a3k 2 a4k 3 a5k 4 Sk ---- = a 1 k ln T k + a 2 k T k + ------ T + ------ T + ------ T + a7k R 2 k 3 k 4 k

The format allows for the specification of a midpoint temperature, where the fits are constrained to match for two temperature ranges. This midpoint temperature may be specified independently for each chemical species. In addition to the temperature-fit coefficients, the thermodynamic data entries define the species elemental composition.
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The species may be composed of a maximum of nine different elements for use with FLUENT/CHEMKIN-CFD.
The data for each species requires four formatted lines, each with a maximum length of 80 characters. Figure A-1 provides a sample of the lines required for entering a set of thermodynamic data. The first two lines in Figure A-1 are required at the top of a thermodynamic database file; the first line identifies the file as containing thermodynamic data, while the second line provides the three temperatures used in the fitting process (a low temperature, break temperature, and high temperature). The remaining input in Figure A-1 consists of four lines for each species containing the elemental composition information and fitting coefficients.
The thermodynamic data is fixed-column format.
Figure A-1
Excerpts from the CHEMKIN therm.dat Thermodynamic Database File
THERMO 300.000 1000.000 5000.000 (CH2O)3 70590C 3H 6O 3 G 0300.00 4000.00 1500.00 0.01913678E+03 0.08578044E-01-0.08882060E-05-0.03574819E-08 0.06605142E-12 -0.06560876E+06-0.08432507E+03-0.04662286E+02 0.06091547E+00-0.04710536E-03 0.01968843E-06-0.03563271E-10-0.05665403E+06 0.04525264E+03 AL 62987AL 1 G 0300.00 5000.00 0600.00 0.02559589E+02-0.10632239E-03 0.07202828E-06-0.02121105E-09 0.02289429E-13 0.03890214E+06 0.05234522E+02 0.02736825E+02-0.05912374E-02-0.04033937E-05 0.02322343E-07-0.01705599E-10 0.03886794E+06 0.04363879E+02 END
1 2 3 4 1 2 3 4
Table A-1 summarizes the rules for thermodynamic data input. Each species includes the species name, the elemental composition of the species, and the temperature ranges over which the polynomial fits to thermodynamic data are valid. The fits to o o o C p R , H RT , and S R consist of seven coefficients for each of two temperature ranges. .
Table A-1 Summary of the Rules for Thermodynamic Data
Line #
1 2
Contents
THERMO (or THERMO ALL)a
Format
Free 3F10.0
Column
Any 1 to 30
Temperature ranges for 2 sets of coefficients: lowest

T, common T, and highest Tb
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Table A-1 Summary of the Rules for Thermodynamic Data
Line #
3
Contents
Species name (must start in Column 1) Date (not used) Atomic symbols and formula Phase of species (S, L, or G for solid, liquid, or gas, respectively) Low temperature High temperature Common temperature (if needed, else blank) Atomic symbols and formula (if needed, else blank) The integer 1 Atomic symbols and formula (if needed, else blank)
Format
18A1 6A1 4(2A1,I3) A1
Column
1 to 18 19 to 24 25 to 44 45
E10.0 E10.0 E8.0 (2A1,I3) I1 4(2A1,I3) 5(E15.8)
46 to 55 56 to 65 66 to 73 74 to 78 80 81 to 100 1 to 75
Coefficients a 1 through a 5 in Equation A-1 through Equation A-3, for upper temperature interval The integer 2
I1 5(E15.8)
80 1 to 75
Coefficients a 6 , a 7 for upper temperature interval, and a 1 , a 2 , and a 3 for lower temperature interval The integer 3
I1 5(E15.8)
80 1 to 60
Coefficients a 4 , a 5 , a 6 , a 7 for lower temperature interval

The integer 4
I1
80
... last
Repeat lines 3 - 6 for each species End (end of thermodynamic data.) Free Any
a.Use THERMO ALL only when included in the chemistry input file and when all thermodynamic data are to be taken from that file. In all other cases use THERMO. b.Include line 2 only with THERMO ALL.
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A.2
Gas-phase Kinetics Input

The GAS-PHASE KINETICS input file includes information on elements, species, thermodynamic data, and the reaction mechanism. Information in the gas-phase kinetics input file is organized in ordered sections. Element data are read first, species data are second, followed by optional thermodynamic data, with reactions specified last. The thermodynamic data for the species may be included in the GAS-PHASE KINETICS input file and/or in a separate Thermodynamic Database file (therm.dat). The syntax for the four types of input is described below.
The description of gas-phase kinetics input in this chapter is identical to that of the CHEMKIN Input manual, Chapter 3. However, there are a few reaction-rate formulations that are not allowed within FLUENT/CHEMKIN-CFD due to the fact that the FLUENT/CHEMKIN-CFD module does not treat plasmas. The specific reaction formulations that have therefore been omitted here are: a) Optional Rate-fit Expressions, b) Radiation Wavelength Parameter, c) Species Temperature Dependence, d) Energy Loss Parameter, and e) Plasma Momentum Collision Frequency Options.
Due to the FLUENT 6.2 limit of 50 user-defined conserved scalars, gas-phase chemistry mechanisms are limited to a maximum of 50 species for use with FLUENT/CHEMKIN-CFD.
In FLUENT, the last species in the list is treated as a background gas and its mass fraction is computed as one minus the sum of the rest of the mass fractions. It is therefore recommended that the last species in the gas-phase chemistry mechanism list be a species that is likely to have a high mass fraction throughout the computational domain.
With the exception of the thermodynamic data, all input is format free, although information outside of column 100 will be ignored.
A.2.1
Element Data
All chemical species in the reaction mechanism must be composed of chemical elements or isotopes of chemical elements. Each element and isotope must be declared as a one- or two-character symbol. The purpose of the element data is to associate atomic weights of the elements with their character symbol representations. For the elements appearing on the periodic chart, the atomic weight (in grams per
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mole) stored internally in the CHEMKIN-CFD module. For isotopes, a one- or twocharacter symbol must be input to identify each isotope, and a symbol and an atomic weight (in grams per mole) for each must be defined. The same symbol must be used in the thermodynamic data to identify the elemental composition of species involving the isotope. Once an isotope has been so defined, it is treated exactly as a new element. If an ionic species is used in the reaction mechanism (i.e., OH+), an electron must be declared as the element E. Element data must start with the word ELEMENTS (or ELEM), followed by any number of element symbols on any number of lines. Element symbols may appear anywhere on a line, but those on the same line must be separated by blanks. Any line or portion of a line starting with an exclamation mark (!) is considered a comment and will be ignored. Blank lines are ignored. If an element is on the periodic chart, then only the symbol identifying the element need appear in the element data.
The elements that CHEMKIN-CFD AND CHEMKIN recognize are as follows: H, HE, LI, BE, B, C, N, O, F, NE, NA, MG, AL, SI, P, S, CL, AR, K, CA, SC, TI, V, CR, MN, FE, CO, NI, CU, ZN, GA, GE, AS, SE, BR, KR, RB, SR, Y, ZR, NB, MO, TC, RU, RH, PD, AG, CD, IN, SN, SB, TE, I, XE, CS, BA, LA, CE, PR, ND, PM, SM, EU, GD, TB, DY, HO, ER, TM, YB, LU, HF, TA, W, RE, OS, IR, PT, AU, HG, TL, PB, BI, PO, AT, RN, FR, RA, AC, TH, PA, U, NP, PU, AM, CM, BK, CF, ES, FM, D, E
For an isotope, the atomic weight must follow the identifying symbol and be delimited by slashes (/). The atomic weight may be in integer, floating-point, or E format, but internally it will be converted to a floating-point number. For example, the isotope deuterium may be defined as D/2.014/. If desired, the atomic weight of an element in the periodic chart may be altered by including the atomic weight as input just as though the element were an isotope. Figure A-2 shows several equivalent ways to describe element information. In this example the elements are hydrogen, oxygen, nitrogen, and the isotope deuterium.
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Figure A-2
Equivalent Ways to Describe Element Information

ELEMENTS H D /2.014/ O N END ! ELEM is equivalent to ELEMENTS
ELEM H D / 2.014 / O N END ELEM H ELEM D/2.014/ ELEM O ELEM
! an END line is optional
Table A-2 summarizes the rules for element data.

Table A-2 Summary of the Rules for Element Data
Rule
1 2 3
Description
The first element line must start with the word ELEMENTS (or ELEM). Element or isotope names are either one- or two-character symbols. An isotope name (i.e., a name not on the periodic chart) must be followed by its atomic weight (in grams per mole) delimited by slashes.
Each element or isotope should be declared only once; however, duplicated element symbols will be ignored.
5 6
An element or isotope name may appear anywhere on the line. Any number of element or isotope names may appear on a line, and more than one line may be used.
Element or isotope names that appear on the same line must be separated by at least one blank space.
An element or isotope name that begins on one line may not continue to the next line.
Any blank spaces between an element or isotope name and the first slash are ignored and any blank spaces between slashes and an atomic weight are also ignored. However, no blank spaces are allowed within an element name or an atomic weight.
10 11
There may be more than one ELEMENT statement. All characters following an exclamation mark are comments.
A.2.2
Species Data
Each chemical species in a problem must be identified on one or more species line(s). Any set of up to 16 upper or lower case characters can be used as a species name. Species names are case sensitive. In addition each species must be composed of elements that have been identified in the element data.
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Species data must start with the word SPECIES (or SPEC), followed by any number of species symbols on any number of lines. Species symbols may appear anywhere on a line, but those on the same line must be separated by blank spaces. Any line or portion of a line starting with an exclamation mark (!) is considered to be a comment and will be ignored. Blank lines are ignored. Figure A-3 shows several equivalent ways to describe species information.
Figure A-3 Equivalent Ways to Describe Species Information
SPECIES SPEC H2 O2 H O OH END SPEC H2 spec O2 H2 O2 H O OH HO2 N2 N NO END
! SPEC is equivalent to SPECIES HO2 N2 N NO
The rules for species data are summarized in Table A-3.

Table A-3 Summary of the Rules for Species Data
Rule
1 2
Description
Species data must start with the word SPECIES (or SPEC). Species names are composed of up to 16-character upper- or lower- case symbols. The names cannot begin with the characters +, =, or a number; an ionic species name may end with one or more + or -.
Each species should be declared only once; however, duplicated species symbols will be ignored.
4 5 6
Each species that subsequently appears in a reaction must be declared. A species name may appear anywhere on the line. Any number of species names may appear on a line, and more than one line may be used.
Species named on the same line must be separated by at least one blank space.
8 9 10
A species name that begins on one line may not continue to the next line. There may be more than one SPECIES statement. All characters following an exclamation mark are comments.
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A.2.3
Thermodynamic Data (Optional)

Any chemical species that appears in a problem must have thermodynamic data associated with it. The data may be extracted from a database file (e.g. therm.dat) and/or read from the GAS-PHASE KINETICS input file. If all the thermodynamic data are to be extracted from a database file, then no thermodynamic data input is required. However, if the user wishes to override information in the database or to provide data on species not in the database, then GAS-PHASE KINETICS input is needed. In any case, the format for the information is the same, and is described in more detail in Chapter A.
When thermodynamic data input is required, it must immediately follow species data.
The first thermodynamic data line must start with the word THERMO (or THER). If all the thermodynamic data are input directly through the GAS-PHASE KINETICS input file, then the first line must read THERMO ALL and the program will not try to open a Thermodynamic database file. For this option the next line must be line 2 of Table A-1. For either option, the subsequent thermodynamic data lines must be in the format of lines 3 - 6 of Table A-1. (For the THERMO option the midpoint temperature is taken from line 2 information already in the Thermodynamic database.) As many species as needed can be included as THERMO input. The following is a summary of the possibilities for specifying thermodynamic data: Case 1: All thermodynamic data from database file
1. A database file is opened (e.g. therm.dat). 2. No THERMO data required as input to the CHEMKIN-CFD Pre-processor. Case 2: Thermodynamic data from database and input files
1. A database file is opened (e.g. therm.dat). 2. Include the following lines in the Chemistry Input File, after the species data:
THERMO Data in Table A-1 format (lines 3 - 6 repeated) for each species not in the database or to override species in database END
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Case 3:
All thermodynamic data from input file
1. No Thermodynamic database file is required. 2. Include the following lines in the Chemistry Input File, after the species data:
THERMO ALL Data in Table A-1 format the species data END (lines 3 - 6 repeated) for at least all species named in
A.2.4
Reaction Data
The reaction mechanism may consist of any number of chemical reactions involving the species named in the species data. A reaction may be reversible or irreversible, it may be a three-body reaction with an arbitrary third body and/or enhanced third body efficiencies, and it may have one of several pressure-dependent formulations.
A.2.4.1
The REACTION line

Reaction data must start with the word REACTIONS (or REAC). On the same line, the user may specify units of the Arrhenius rate coefficients [Equation B-5] to follow by including the word CAL/MOLE, KCAL/MOLE, JOULES/MOLE, KJOULES/MOLE, KELVINS, or EVOLTS for E i , and/or MOLES or MOLECULES for A i . If MOLECULES is specified, then the units for A i are cm, molecules, sec and K.
If units are not specified, A i and E i must be in cm, mole, sec, K and cal/mole, respectively. Note that T is always in Kelvin.
Also on the REACTION line, the user may indicate that a user-written rate routine will be used to over-ride the species rates-of-production calculations, by including the word USRPROD. This would over-ride any other reaction input in the GAS-PHASE KINETICS input file. The USRPROD input optionally includes a slash(/)-delimited integer parameter, which allows the user to distinguish one reaction model from another within their user routine. When the USRPROD parameter is included, CHEMKIN-CFD will call a usersupplied subroutine, CKUPROD wherever net species production rates are required. A template of CKUPROG can be obtained from Reaction Design as well as information about how to compile and link user routines into FLUENT/CHEMKIN-CFD.
Reaction Design does not support user-written programming, so you are cautioned to use this feature at your own risk.
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A.2.4.2
Reaction Strings and Rate Coefficients

The lines following the REACTION line contain reaction descriptions together with their Arrhenius rate coefficients. The reaction description is composed of reaction data and optional auxiliary information data. Each reaction line is divided into two fields. The first contains the symbolic description of the reaction while the second contains the Arrhenius rate coefficients. Both fields are format free and blank spaces are ignored. Any line or portion of a line starting with an exclamation mark (!) is considered a comment and is ignored. Blank lines are ignored. The reaction description, given in the first field, must be composed of the species symbols, coefficients, delimiters, and any special symbols defined in Table A-4.
Table A-4 Reaction Data Criteria Species Symbols Each species in a reaction is described with the unique sequence of characters as they appear in the species data and the thermodynamic data (e.g. H2). Coefficients A species symbol may be preceded by an integer or real coefficient. The coefficient has the meaning that there are that many moles of the particular species present as either reactants or products; e.g. 2OH, is equivalent to OH + OH. Non-integer coefficients are allowed in GASPHASE KINETICS,
but the element balance in the reaction must still be maintained.
Delimiters + A plus sign is the delimiter between each reactant species and each product species. = An equality sign is the delimiter between the last reactant and the first product in a reversible reaction. <=> An equality sign enclosed by angle brackets can also be used as the delimiter between the last reactant and the first product in a reversible reaction. => An equality sign with an angle bracket on the right is the delimiter between the last reactant and the first product in an irreversible reaction
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Table A-4 Reaction Data Criteria Special Symbols +M An M as a reactant and/or product stands for an arbitrary third body. It should appear as both a reactant and a product. In a reaction containing an M, species can be specified to have enhanced third body efficiencies, in which case auxiliary information data (described below) must follow the reaction line. If no enhanced third body efficiencies are specified, then all species act equally as third bodies and the effective concentration of the third body is the total concentration of the mixture. (+M) An M as a reactant and product surrounded by parentheses indicates that the reaction is a pressure-dependent reaction, in which case auxiliary information line(s) (described below) must follow the reaction to identify the fall-off formulation and parameters. A species may also be enclosed in parenthesis. Here, for example, (+H2O) indicates that water is acting as the third body in the fall-off region, not the total concentration M. ! An exclamation mark means that all following characters are comments on the reaction line. For example, the comment may be used to give a reference to the source of the reaction and rate data.
The second field of the reaction line is used to define the Arrhenius rate coefficients A i , i , and E i , in that order, as given by Equation B-5. At least one blank space must separate the first number and the last symbol in the reaction. The three numbers must be separated by at least one blank space, be stated in either integer, floating point, or E format (e.g., 123, 123.0 or 123E1), and have units associated with them.
Unless modified by the REACTION line, the default units for A i are in cgs (cm, sec, K, mole), the exact units depending on the reaction. The factor i is dimensionless. The default units for the activation energies are cal mole .
Examples of reaction data are shown in Figure A-4.

Figure A-4 Examples of Reaction Data.
REACTIONS 2 + O2 = 2OH ! H2 + O2 = OH + H H + O2 + M = HO2 + M ! H + O2 + M = HO2 ! H + O2 = HO2 + M OH+ + H + E = H2O O + HV = O(*) 0.5H2 + 0.5O2 = OH END CAL/MOLE 1.7E13 0 47780. ! Ref. 21 1.7E13 0 47780. ! same as previous reaction, ! commented to prevent a duplication error 2.0E15 0.000 -870. 2.0E15 0.000 -870. 2.0E15 0.000 -870. 1.E19 0 0.0 1.3A5 0 0 ! example of real coefficients ! END statement is optional; ! <eof> condition is equivalent
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Table A-5 is a summary of the gas-phase reaction data rules.

Table A-5 Summary of the Rules for Gas-phase Reaction Data
Rule
1
Description
The first reaction line must start with the word REACTIONS (or REAC), and may include units definition(s).
The reaction description can begin anywhere on the line. All blank spaces, except those between Arrhenius coefficients, are ignored.
Each reaction description must have =, <=> or => between the last reactant and the first product.
4 5
Each reaction description must be contained on one line. Three Arrhenius coefficients must appear in order ( A i , i , and E i ) on each Reaction line, separated from each other and from the reaction description by at least one blank space; no blanks are allowed within the numbers themselves.
6 7
There cannot be more than six reactants or six products in a reaction. Comments are any and all characters following an exclamation mark.
A.2.4.3
Auxiliary Reaction Data

The format of an auxiliary information line is a character-string keyword followed by a slash-delimited (/) field containing an appropriate number of parameters (either integer, floating point, or E format).
A.2.4.3.1
Neutral Third Body Efficiency If a reaction contains M as a reactant and/or product, auxiliary information lines may follow the reaction line to specify enhanced third body efficiencies of certain species (i.e., aki, Equation B-12). To define an enhanced third body efficiency, the keyword is the species name of the third body, and its one parameter is the enhanced efficiency factor of that species. A species that acts as an enhanced third body must be declared as a species. Examples of third body efficiencies are shown in the first three reactions in Figure A-5. Pressure Dependent Reaction Parameters If a pressure-dependent reaction is indicated by a (+M) or by a species contained in parentheses, say (+H2O), then one or more auxiliary information lines must follow to define the pressure-dependence parameters. In this section we describe formulations where a fixed functional form is described for the pressure interpolation between a
A.2.4.3.2
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high-pressure limit and low-pressure limit defined by Arrhenius coefficients. The user has several options for defining the functional form and the parameters that describe its shape. The user may also want to consider Section A.2.4.3.3 and Section A.2.4.3.4 for alternative methods in describing pressure dependence. For the formulations described here, the Arrhenius coefficients on the reaction line are for the high-pressure limit ( A , , and E ) for unimolecular fall-off reactions and represent the low-pressure limit ( A o , o , and E o ) for chemically activated bimolecular reactions (see the description of these reaction types in Section B.1.3). For all such pressure-dependent reactions, an auxiliary information line must follow to specify either the low-pressure limit Arrhenius parameters (for fall-off reactions) or the highpressure limit Arrhenius parameters (for chemically activated reactions). For fall-off reactions, the keyword LOW must appear on the auxiliary information line, with three rate parameters A o , o , and E o (Equation B-14). For chemically activated bimolecular reactions, the keyword HIGH must appear on the auxiliary information line, with the three rate parameters A , , and E (Equation B-15). There are then three possible interpretations for the functional form of the pressure dependence for these types of reactions: 1. To define the Lindemann6 formulation of a pressure-dependent reaction, no additional parameters are defined. 2. To define a Troe7 pressure-dependent reaction, in addition to the LOW or HIGH parameters, the keyword TROE followed by three or four parameters must be included in the following order: a, T***, T*, and T** (Equation B-22). The fourth parameter is optional and if omitted, the last term in Equation B-22 is not used. 3. To define an SRI pressure-dependent reaction8, in addition to the LOW or HIGH parameters, the keyword SRI followed by three or five parameters must be included in the following order: a, b, c, d, and e (Equation B-23). The fourth and fifth parameters are options. If only the first three are stated, then by default d = 1 and e = 0 . Examples of these options are shown in Figure A-5.
6.F. Lindemann, Trans. Faraday Soc. 17:598 (1922). 7.R. G. Gilbert, K. Luther, and J. Troe, Ber. Bunsenges. Phys. Chem. 87:169 (1983). 8.P. H. Stewart, C. W. Larson, and D. M. Golden, Combustion and Flame 75:25 (1989).
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A.2.4.3.3
Chebyshev Polynomial Rate Expressions A Chebyshev reaction is similar to other pressure-dependent reactions described in Section A.2.4.3.2, in that it is indicated by a (+M) as a reactant and product. To specify Chebyshev polynomial implementation, the keyword CHEB must be included after the reaction line, and followed by any number of parameters. There may be multiple CHEB lines required for a given reaction. Following the CHEB line, the first parameter given must be N, the number of basis functions along the temperature axis. The second parameter must be M, the number of basis functions along the pressure axis. The remainder of the parameters must be the N M coefficients anm from Equation B-29, in the order of a11, a12, ..., a1M, a21, ..., anm. To specify the temperature limits, the keyword TCHEB must be followed by Tmin and Tmax, otherwise the default limits are 300 K and 2500 K, respectively. To specify pressure limits, the keyword PCHEB must be followed by P min and P max , otherwise the default limits are 0.1 atm and 100 atm, respectively. See Figure A-5 for an example of Chebyshev polynomial input. Pressure Dependence Through Logarithmic Interpolation This generalized way of describing the pressure dependence of a reaction rate is indicated by the use of the PLOG keyword in auxiliary lines. In this case, the reaction description should not include (+M) in it, although this is used to indicate that the reaction is pressure dependent in other cases. This option for describing pressure dependent reactions can not be combined in any given reaction with other options for describing pressure dependence. One supplementary line starting with the PLOG keyword needs to be supplied for each pressure in the set. The keyword is followed by slash-delimited values for the pressure (in atmospheres) and the rate parameters for that pressure. The supplementary lines need to be in order of increasing pressure. If the rate expression at a given pressure cannot be described by a single set of Arrhenius parameters, more than one set may be provided. These will be treated as DUPLICATE reactions, meaning the sum of the sets of rates provided for a given pressure will be used. The units of the rate parameters provided with the PLOG keyword should match the units used for the overall reaction description. Note that in this case, although rate parameters need to be supplied on the main reaction line to prevent an error, those values are superseded by the ones provided on the supplementary lines. Landau-Teller Reactions To specify Landau-Teller parameters, the keyword LT must be followed by two parametersthe coefficients B i and C i from Equation B-31. The Arrhenius parameters A i , i , and E i are taken from the numbers specified on the reaction line itself. If reverse parameters are specified in a Landau-Teller reaction by REV (see Section A.2.4.3.6), the reverse Landau-Teller parameters must also be defined, with the keyword RLT and two coefficients B i and C i for the reverse rate.
A.2.4.3.4
A.2.4.3.5
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A.2.4.3.6
Reverse Rate Parameters For a reversible reaction, auxiliary information data may follow the reaction to specify Arrhenius parameters for the reverse-rate expression. Here, the three Arrhenius parameters ( A i , i , and E i ) for the reverse rate must follow the keyword REV. This option overrides the reverse rates that would be normally computed by satisfying microscopic reversibility through the equilibrium constant, Equation B-6. Reaction Order Parameters Auxiliary data may be included to override the reaction order for a species, using the auxiliary keywords FORD or RORD, for forward and reverse reaction descriptions, respectively. Each occurrence of these keywords must be followed by the species name and the new reaction order. This option overrides the values of ki and ki in Equation B-4, for the species included in the auxiliary data. Reaction Units It is sometimes convenient to specify the units for a particular reaction rate fit that may differ from the default units specified for other reaction expressions in the chemistry mechanism. In this case, the user employs the auxiliary keyword UNITS. This keyword must be followed by one or more of the following unit descriptors: MOLE(CULE), CAL, KCAL, JOUL, KJOU, KELV(IN), or EVOL(TS), where the letters in parentheses are optional. The inclusion of MOLE(CULE) would indicate that the reaction rate expression is in units of molecules/cm3 rather than mole/cm3. The remaining unit descriptors specify the units of the energy E i in the rate expression. Note that the units of T in the rate expression are always in Kelvin. Duplicate Reaction Descriptions It sometime happens that two or more reactions can involve the same set of reactants and products, but proceed through distinctly different processes. In these cases, it may be appropriate to state a reaction mechanism that has two or more reactions that are the same, but have different rate parameters. However, duplicate reactions are normally considered errors by the Pre-processor. If the user requires duplication (e.g., the same reactants and products with different Arrhenius parameters), an auxiliary information statement containing the keyword DUP (with no parameters) must follow the reaction line of each duplicate reaction (including the first occurrence of the reaction that is duplicated). For example, if the user wishes to specify different rate expressions for each of three identical reactions, there must be three occurrences of the DUP keyword, one following each of the reactions. Any number of auxiliary information lines may follow a reaction line, in any order, and any number of keywords or enhanced third bodies may appear on an auxiliary information line; however, a keyword and its parameter(s) must appear on the same line.
A.2.4.3.7
A.2.4.3.8
A.2.4.3.9
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Examples of equivalent ways to state auxiliary information are shown in Figure A-5. The above rules are summarized in Table A-6. A.2.4.3.10 Optional User Rate Subroutine CKUPROG The auxiliary keyword USRPROG, optionally appended by a slash(/)-delimited integer parameter, implies that the net rate of progress for the reaction will be obtained by calling a user-supplied subroutine, CKUPROG. The optional parameter allows the user to select from more than one type of rate formulation. Wherever the net reaction rate is required, it will be obtained by calling the user-written subroutine. USRPROG applies only to irreversible reactions, and cannot be used in conjunction with USRPROD (entered on the REACTION line). A template of CKUPROG can be obtained from Reaction Design as well as information on how to compile and link user routines into FLUENT/CHEMKIN-CFD.
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Figure A-5
Examples of Gas-phase Auxiliary Information Data

REACTIONS HCO+M=H+CO+M CO/1.87/ H2/1.87 CAL/MOLE 0.250E+15 0.000 16802.000 CH4/2.81/ CO2/3./ H2O/5./ 0.000 2066.000 ! Warnatz
H+C2H4(+M)=C2H5(+M) 0.221E+14 LOW / 6.369E27 -2.76 -54.0 / H2/2/ CO/2/ CO2/3/ H2O/5/ CH3+CH3(+M)=C2H6(+M)9.03E16 -1.18 LOW / 3.18E41 -7.03 2762 / TROE / 0.6041 6927. 132. / H2/2/ CO/2/ CO2/3/ H2O/5/ CH3+H(+M)=CH4(+M)6.0E16 -1.0 0.0 LOW / 8.0E26 -3.0 0.0/ SRI / 0.45 797. 979. / H2/2/ CO/2/ CO2/3/ H2O/5/
! Michael !Lindemann fall-off reaction ! enhanced third-body efficiencies
654. ! TROE fall-off reaction, with 3 parameters ! enhanced third-body efficiencies
! SRI fall-off reaction ! enhanced third-body efficiencies 10600.0! Stewart ! Chemically activated reaction ! SRI pressure dependence 1.190E4 ! Westbrook
CH3+CH3(+M)=H + C2H5(+M)4.989E12 0.099 HIGH/ 3.80E-7 4.838 7710. / SRI / 1.641 4334 2725 / CH4+H=CH3+H2 REV / 4.80E12 1.25E14 1.143E4 / 0
! The following two reactions are acceptable duplicates: H2+O2 = 2OH DUPLICATE H2+O2 = 2OH DUPLICATE H2(1)+H2O(000)=H2(0)+H2O(001) LT / -67 62.1/ 1.7E13 1.0E13 0 0 47780 47000.
2.89E15
0 ! Landau-Teller reaction
! The following is a Chebyshev polynomial rate description C2H5 + O2 (+M) <=> C2H4E + HO2 (+M) 1.00E+00 .000 0. TCHEB/ 300 2500/ PCHEB/1 100/ CHEB/ 7 3 1.0216E+01 -1.1083E+00 -1.9807E-01 7.8325E-01/ CHEB/ 1.1609E+00 1.1762E-01 -9.5707E-02 1.0928E-01 1.1551E-01/ CHEB/ -8.0290E-02 -1.0978E-01 3.7074E-04 -1.4830E-02 -6.0589E-02/ CHEB/ -2.8056E-02 6.9203E-03 -9.7259E-03 -1.3556E-02 7.6648E-03/ CHEB/ 6.6865E-03 -8.8244E-04/ H2O+H = OH+H2 FORD /H2O 1.1/ END 0.117E+10 1.30 3626 ! Bozzelli
!END line is optional
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Table A-6 summarizes the rules for Auxiliary Information Data.

Table A-6 Summary of the Rules for Gas-phase Auxiliary Information Data
Rule
1
Description
Auxiliary information lines may follow reaction lines that contain an M to specify enhanced third-body efficiencies, a reaction that contains an HV to specify the radiation wavelength, a reversible reaction to specify the reverse rate parameters explicitly, or any reaction that specifies Landau-Teller parameters. Auxiliary information must follow any duplicate reactions as well as all reactions that indicate pressure-dependent behavior by (+M) (i.e., provide fall-off parameters).
A species may have only one enhanced third-body efficiency associated with it in any one reaction.
3 4
Only one radiation wavelength may be declared in a reaction. The order in which the enhanced third-body declarations are given is the order in which arrays of enhanced third-body information are referenced in the subroutine package.
5 6 7
There cannot be more than ten enhanced third-bodies in a reaction. Keyword declarations may appear anywhere on the line, in any order. Any number of keywords may appear on a line and more than one line may be used; however, a keyword and its parameter(s) must appear on the same line.
Keyword declarations that appear on the same line must be separated by at least one blank space.
Any blank spaces between a keyword and the first slash are ignored and any blanks between the slashes and parameter(s) are also ignored. However, no blank spaces are allowed within a keyword or a parameter.
10
All characters following an exclamation mark are comments.
A.2.4.4
Problems Having No Reactions

In some problems, only information about the elements and species is needed (e.g., when surface chemistry is dominant). In such cases, it is not necessary to include reaction data. The CHEMKIN-CFD pre-processor will proceed to store only element, species, and thermodynamic data when no reaction data is found in the GAS-PHASE KINETICS input file.
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A.2.5
Error Checks
The CHEMKIN-CFD Pre-processor checks each input line for proper syntax and writes diagnostic messages if errors are encountered. The input must be error free before the FLUENT/CHEMKIN-CFD program may be run. The possibilities for an error condition are listed Table A-7.
Table A-7 Error Checks
Data Type
Element
Possible Errors
Atomic weight for an element or isotope is not declared, and the element is not found in the internal database. Atomic weight has been declared, but not enclosed by two slashes (/). If an element is declared twice, a diagnostic message is printed, but the duplicate is simply eliminated from consideration and is not considered a fatal error.
Species
If a species is declared twice, a diagnostic message is printed, but the duplicate is eliminated from consideration and is not considered a fatal error. No thermodynamic data have been found for a declared species.
Thermodynamic
Thermodynamic data are format sensitive and therefore provide possibilities for error if not formatted exactly as described by Table A-1. An element in the thermodynamic data for a declared species has not been included in the element data. With the THERMO ALL option, line 2 (Table A-1) is not found.
Reaction
A delimiter =>, <=>, or = between the reactants and the products is not found. Three Arrhenius parameters are not found. Reactants and/or products have not been properly delineated by a plus sign (+). A species as a reactant or product has not been declared in the species data. The reaction does not balance in elements. The reaction does not balance in electronic charge. A reaction is a duplicate not declared by the auxiliary data keyword DUP. A third-body species enclosed in parentheses in a fall-off reaction appears as reactant or product, but not both.
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Data Type
Possible Errors
A species is a third-body in a fall-off reaction, and +M also appears in the reaction. More than one +M or third body appear as reactants and/or products.
HV declared body as a reactant and as a product.
There are more than six reactants or six products. Auxiliary There is an unknown or misspelled keyword or enhanced third-body species name. Parameters for a keyword are not enclosed in slashes. The wrong number of parameters appear for a keyword. There are duplicate keywords for a reaction.
LOW, HIGH, TROE, SRI, PCHEB, TCHEB, or CHEB are found after a reaction that did not have a species or M in parentheses. LOW, HIGH, or CHEB is not found after a pressure-dependent reaction.
A combination of TROE, SRI, and/or CHEB is found.

LT and REV are found for a Landau-Teller reaction, but RLT is not found. LT is given for a fall-off reaction.
There are more than ten enhanced third bodies.

USRPROG given for a USRPROD mechanism. USRPROG given for a reversible reaction.
A.3
Surface Kinetics Input

The SURFACE KINETICS input file includes information about surface sites (phases), surface site species, bulk phases, bulk species, thermodynamic data, and the surface reaction mechanism. At the beginning of the file, a user may specify an optional material name. This is followed by site data, then by bulk data. Thermodynamic data may follow these phase and species data, and reaction data are specified last. Each of these sections of data are optional. Such sets of information can be repeated for any number of different materials, although the FLUENT/CHEMKIN-CFD package can only handle one surface-chemistry material at a time for a given simulation. The thermodynamic data for the species may be included in the SURFACE KINETICS input file and/or from a Thermodynamic Database file (e.g., therm.dat).
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The description of surface kinetics input in this chapter is identical to that of the CHEMKIN Input manual, Chapter 4. However, there are a few reaction-rate formulations that are not allowed within FLUENT/CHEMKIN-CFD due to the fact that the FLUENT/CHEMKIN-CFD module does not treat plasmas. Specific reaction formulations that have therefore been omitted here are: a) Bohm Velocity Limit for Ions, b) Ion-energy Dependent Rates, and c) Ion-energy Dependent Yield. In addition, FLUENT/CHEMKIN-CFD does not currently allow treatment of multiple materials.
The syntax for the four types of input is described in this section. With the exception of the thermodynamic data, all input is format free, although data outside of columns 180 will be ignored.
A.3.1
Material Declaration
Entirely different surface reaction mechanisms (i.e., with different surface and bulk phases and species, and different surface reactions) can be specified in the same SURFACE KINETICS input file through the use of multiple materials. At the beginning of each separate portion of the input file corresponding to a given material, the user may include a line with the keyword MATERIAL followed by an optional slash-delimited material name. If no name for the material is supplied, a default name, MATERIALn, will be substituted, where n is the number of the material (e.g., MATERIAL2 for the second material given in an input file).
A.3.2
Site Data
Surface-phase species exist on sites, and a site and its species must be identified on one or more lines of site data. The first line in a set of site data must start with the word SITE; an optional name may be associated with a site if it immediately follows SITE and is delimited by slashes(/). If no name for the site is supplied, the default name SITEn is assumed, where n is the number of a site (e.g., SITE2 for the second site type listed). Following SITE and/or the site name, the word SDEN and a slashdelimited density (the standard-state site density for this site, in mole/cm2) for the site is required. The species that can reside on the site type are declared by a list of species symbols (names) on the same line or on additional lines.
The name of a site species must not duplicate the name of a gas-phase species or a bulk species, and must be unique among the site species.
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An optional slash-delimited site occupancy number may follow a species name. This represents the number of individual sites that this species occupies. For example, a large chemical species might cover two or more sites. The default site occupancy for a surface species is 1. The sets of SITE data input can continue for as many site types as are needed. Any set of up to sixteen upper- or lower-case characters can be used as a site name or species symbol. In addition, each species must be composed of elements that have been identified in the GAS-PHASE KINETICS input file. One of the primary purposes of the site data is to define the order in which arrays of site species information are referenced in the CHEMKIN-CFD module.
Species symbols may not begin with a number, a plus sign (+), a pound sign (#), or an equality sign (=), have imbedded blanks, or include a slash (/). An ionic species may end with any number of plus or minus signs; an imbedded plus sign must be enclosed in parentheses.
Any line starting with or any portion of a line following an exclamation mark (!) is considered a comment and will be ignored. Blank lines are also ignored. Figure A-6 shows sample site data. The rules for site data are summarized in Table A-8.
Figure A-6 Examples of Site Data
SITE / PLANE / SDEN/1.04E-9/ ASH(V) ASH2(V) ASH3(V) H(S) CH3(V) AS(V) AS2(V)/2/ V END SITE / LEDGE / SDEN/1.66E-10/ GACH(L) DMG(L)/2/ L SITESDEN/1.0E-10/ GA(S) ! PLANAR SITE ! FIRST SPECIES ON PLANE SITE ! ! ! ! ! ! ! ! EMPTY PLANAR SITE AN END STATEMENT IS OPTIONAL LEDGE SITE FIRST SPECIES ON LEDGE THIS SPECIES OCCUPIES 2 SITES EMPTY LEDGE SITE SITE WITH ONLY ONE SPECIES SITE NAME NOT INCLUDED
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Table A-8 Summary of the Rules for Site Data
Rule
1
Description
Site data must start with a line containing the word SITE, followed by an optional slash-delimited name (i.e., SITE/name/).
The standard-state site density is required as a slash-delimited number (in
mole/cm2) following the word SITE and/or the site name, and preceded by the
word SDEN. 3 The site density is followed by one or more site species name declarations. Declaring a site with no site species is an error. 4 Site and species names are composed of up to sixteen upper- or lower-case character symbols. The names cannot begin with the characters +, =, #, or a number; an ionic species name may end with one or more + or - signs; an embedded plus sign must be enclosed in parentheses (+). Names cannot include a slash (/). 5 All species names should be unique; duplicate species names will be ignored and a warning issued. A species name may not duplicate a name of a gas-
phase species, another surface species, or a bulk species.

6 A site name must not duplicate the name of any other phase (gas, surface site, or bulk phase). 7 Each surface species that subsequently appears in a surface reaction must have been declared in this section. 8 9 A site species name may appear anywhere on the line. A site species may have a slash-delimited site occupancy (the number of sites that this species occupies on the surface) following the species name. 10 A species name declaration that begins on one line may not continue to the next line (i.e., do not break a species name into two lines). 11 12 There may be more than one set of SITE data. All characters on a line following an exclamation mark are considered comments. 13
SITE data are not required.
A.3.3
Bulk Data
A set of bulk data may consist of one or more condensed-phase species. The first line in a set of bulk data must start with the word BULK and may be followed by an optional slash-delimited name for the bulk phase. If a name is not supplied for bulk phase n , then the name BULKn is supplied by the Pre-processor. Bulk species are declared by a
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list of unique species symbols (names) on the same line or on additional lines. An optional slash-delimited density (in g/cm3) may follow a species name. If no density is supplied, the unphysical value of -1.0 is stored as a flag. The rules for bulk species symbols (names) are essentially the same as those for site species. Figure A-7 shows sample bulk data. The rules for bulk data are summarized in Table A-9.
Table A-9 Summary of the Rules for Bulk Data
Rule
1
Description
Bulk data must start with a line containing the word BULK, and may be followed by a slash-delimited name for the bulk phase (i.e., BULK/name/).
The BULK declaration and/or bulk name must be followed by one or more bulk species declarations. Declaring a bulk phase with no bulk species is an error.
Bulk and bulk species names are composed of up to sixteen upper- or lowercase character symbols. The names cannot begin with the +, =, #, or a number; an ionic species name may end with one or more + or - signs; an embedded plus sign must be enclosed in parentheses (+). Names cannot include a slash (/).
All species names should be unique; duplicate species names will be ignored and a warning issued. A species name may not duplicate a name of a gas-
phase species, a surface species, or another bulk species.

5 All phase names must be unique. For example, a bulk phase name may not duplicate the name of any other phase (gas, surface site, or bulk phase). 6 Each bulk species that subsequently appears in a surface reaction must have been declared in this section. 7 8 A bulk species declaration may start anywhere on the line. A bulk species name may be followed by an optional slash-delimited mass density (in g/cm3). 9 A bulk species declaration that begins on one line may not continue to the next line (i.e., do not break species names into two lines). 10 11 There may be more than one set of BULK data. All characters on a line following an exclamation mark are considered comments and are ignored. 12
BULK data are not required.
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Figure A-7
Examples of Bulk Data

BULK / GA_RICH / BULK / GA_RICH / GA2AS(1)/3.0/ GA3AS(1)/3.0/ GA2AS(1)/2.0/ BULK AS(B) END GA2AS(1)/3.0/ GA3AS(1)/3.0/ END !an END statement is optional
!THIS NAME IS A DUPLICATE AND WILL BE IGNORED !BULK PHASE WITH NO NAME SUPPLIED !ONLY ONE BULK SPECIES AND NO DENSITY SUPPLIED
A.3.4
Thermodynamic Data
Any chemical species that appears in a problem must have thermodynamic data associated with it. This data is used in evaluation of thermodynamic properties (entropy, enthalpy, heat capacity) and reverse reaction rate constants through the equilibrium constant. Often thermodynamic data for a species, for instance a surface species, is unknown. Such data can sometimes be calculated via theoretical techniques. However, the user can work around the need for actual thermodynamic data for all species by making the reactions irreversible. In this case, the user can provide dummy thermodynamic data for the surface species to satisfy the SURFACE KINETICS input requirement and supply the elemental composition of the surface species.
If every reaction in the mechanism is either irreversible, or if Arrhenius rate parameters are given explicitly for the reverse reaction, then the thermodynamic data for species are not actually used for anything related to the kinetics. However, they may be used for determining heat-capacity or energy-balance effects involving the surface.
Thermodynamic data may be extracted from a database file (therm.dat) and/or read from the SURFACE KINETICS input file. If all the thermodynamic data are extracted from the database, then no thermodynamic data are required from the input file. However, if the user wishes to override information in the database or provide data on species not in the database, then thermodynamic input is needed in the SURFACE KINETICS input file. In any case the format for the information is the same, and is described in detail in Chapter A. When thermodynamic data input is required, it must immediately follow species data (SITE and BULK data). The first thermodynamic data line must start with the word THERMO (or THER). If all the thermodynamic data are input directly to the Pre-processor, then the first line of this section must read THERMO ALL and the program will not expect a Thermodynamics Database file; for this option the next line must be line 2 of Table A-1. For either option, the subsequent thermodynamic data lines must be in the format of lines 3 - 6 of Table A-1. (For the THERMO option the default midpoint
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temperature is taken from the second line of information already in the Thermodynamic Database.) The THERMO input can include as many species as are needed. Thermodynamic data for any species that were not declared in the SITE and BULK sections will be ignored. The cases for the thermodynamic data section are the same as those described in Section A.2.3 for GAS-PHASE KINETICS input.
A.3.5
Surface Reaction Mechanism Description

The surface reaction mechanism may consist of any number of chemical reactions involving the solid species named in the site and bulk data, as well as the gas-phase species declared in the GAS-PHASE KINETICS Pre-processor. A reaction may be reversible or irreversible.
A.3.5.1
The REACTION Line

Reaction data must start with the word REACTIONS (or REAC). On the same line the user may specify units of the Arrhenius rate coefficients to follow by including the words CAL/MOLE, KCAL/MOLE, JOULES/MOLE, KJOULES/MOLE, EVOLTS, or KELVINS to indicate the units for all rate parameters that have energy units, e.g., the activation energy E i of Equation B-47.
Even if the default energy units are changed by giving one of the REACTION line keywords, the temperature appearing in the Arrhenius expression of Equation B-47, i.e., in T raised to the
power and in the denominator of the activation energy term, is always in Kelvins.
The special words MOLES or MOLECULES can appear on the REACTIONS line to indicate the units for A i (see Equation B-61). If MOLECULES is specified, then the units for A i are based on cm, molecules, sec or K.
If units are not specified, A i and E i are assumed to be in cm, mole, sec. K and cal/mole, respectively.
In addition to controlling the units options of the rate coefficients, the user may also include a keyword on the REACTIONS line to control the way that sticking coefficients are converted to reaction-rate coefficients. In particular, the user may enable or disable the Motz-Wise9 correction factor, (see Equation B-61), which is off by default. The keyword MWON can be included on the REACTIONS line to turn on this correction for all reactions that are specified as sticking-coefficient reactions. Alternatively, the user
9.H. Motz and H. Wise, Journal of Chemical Physics 32:1893 (1960).
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may include MWON as an auxiliary keyword following an individual reaction to turn on the Motz-Wise correction for that reaction only, as discussed in Section A.3.5.3.4. Conversely, if the MWON parameter was given on the REACTION line, the user can include the MWOFF auxiliary keyword following an individual reaction, specifying that the MotzWise correction is to be used for that reaction only. MWOFF is the default.
We recommend that the user leave the Motz-Wise9 (p. 63) correction off in the conversion between a sticking coefficient and a rate constant, which is the default.
Finally, on the REACTIONS line, the user may specify USRPROD to indicate that the user will provide a user-written rate routine that will supply all of the species net rates of production, overriding any other reaction input in the SURFACE KINETICS input file. The USRPROD input optionally includes a slash(/)-delimited integer parameter, which allows the user to distinguish one reaction model from another within their user routine. When the USRPROD parameter is included, CHEMKIN-CFD will call a user-supplied subroutine, SKUPROD wherever net species production rates are required. A template of SKUPROD can be obtained from Reaction Design as well as information on how to compile and link user routines into FLUENT/CHEMKIN-CFD.
Reaction Design does not support user-written programs, so you are cautioned to use this feature at your own risk.
The lines following the REACTION line contain reaction descriptions together with their Arrhenius rate coefficients. The reaction description is composed of reaction data and optional auxiliary information data.
A.3.5.2
Surface Reaction Data

Each reaction line is divided into two fields, where a line may take up two or more physical lines if it is more than 80 characters long. A reaction data entry is continued on the next line using the special character & at the end of the line; any information following the & symbol on the same line is ignored. The first field in the reaction entry contains the symbolic description of the reaction, while the second contains the Arrhenius rate coefficients. Both fields are format free, and blank spaces are ignored. All characters on a line following an exclamation mark (!) are considered comments and are ignored. Blank lines are also ignored.
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The reaction description, given in the first field, must be composed of the species symbols, coefficients, and delimiters as summarized below.
Table A-10 Surface Reaction Data Criteria Species Symbols Each species in a reaction is described with the unique sequence of characters as they appear in the species data and the thermodynamic data. Coefficients A species symbol may be preceded by an integer or real coefficient. The coefficient has the meaning that there are that many moles of the particular species present as either reactants or products; e.g., 2OH is equivalent to OH +OH. This is explained in Section A.3.5.3. Delimiters + A plus sign is the delimiter between each reactant species and each product species. = An equality sign is the delimiter between the last reactant and the first product in a reversible reaction. <=> An equality sign enclosed by angle brackets can also be used as the delimiter between the last reactant and the first product in a reversible reaction. => An equality sign with an angle bracket on the right is the delimiter between the last reactant and the first product in an irreversible reaction.
The second field of the reaction line is used to define the Arrhenius rate coefficients A i , i , and E i in that order, as given by Equation B-47. At least one blank space must separate the last species name in the reaction and first number. The three numbers must be separated by at least one blank space, be stated in either integer, floating point, or E format (e.g., 123 or 123.0 or 12.3E1), and have units associated with them (although the units do not appear on the input line).
Unless modified by the REACTIONS line or by the UNITS auxiliary keyword, the default units for factor i is dimensionless. The default units for the activation energies are cal/mole.
A i are cgs (cm, sec, K, mole), the exact units depending on the order of the reaction. The
The second field of the reaction line may optionally be used to specify the coefficients a i , b i , and c i of Equation B-59 for a sticking coefficient. In order for the second field to apply to sticking coefficient parameters, the next line of input must contain the auxiliary keyword STICK.
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Examples of some reaction data are shown in Figure A-8. Table A-11 summarizes the reaction data rules.
Figure A-8 Examples of Surface Reaction Data
REACTIONS KCAL/MOLE
ASH3 + AS(P) <=> ASH3(P) + AS(D) 4.0E11 0 25 ! Ref. 21 ! ASH3 + AS(P) <=> ASH3(P) + AS(D) 4.0E11 0 0 ! same as previous ASH <=> AS(D) + H(S) 1.0 0 0 STICK GA(CH3)3(L) + GA2AS(A) <=> AS + GA(CH3)(L) + 2 GAME & ! continued on next line 1.0E13 0 4000.
Table A-11 Summary of the Rules for Surface Reaction Data
Rule
1
Description
The first reaction line must start with the word REACTIONS (or REAC), and may be followed by units definition(s), the word MWOFF. The word MWON can be used to turn on the Motz-Wise9 (p. 63) correction of
Equation B-61, for all sticking-coefficient reactions, or the word MWOFF can be
used to specify that the Motz-Wise correction will not be used for all stickingcoefficient reactions (the default). Including MWON or MWOFF as an auxiliary keyword for an individual reaction (discussed later) will override the setting given on the REACTION line. 3 Valid unit declarations are EVOLTS, KELVINS, CAL/MOLE, KCAL/MOLE,
JOULES/MOLE, KJOULES/MOLE, MOLES, and MOLECULES.
The reaction description can begin anywhere on this line. All blank spaces, except those separating the Arrhenius coefficients, are ignored.
Each reaction description must have =, <=>, or => between the last reactant and the first product.
Each species in a reaction is described with a unique sequence of characters (name) as they appear in the species data and the thermodynamic data. However, if a species name is not unique (because it is duplicated in another phase), the name must be modified by appending its slash-delimited phase name, i.e. as name/phase/.
Stoichiometric coefficients are represented by an integer or real number preceding a species name. The default is to assume a stoichiometric coefficient of 1.
A reaction description may be contained on more than one line. If a line contains the symbol &, all information following the & symbol will be ignored and the next line will be considered a continuation of the first.
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Table A-11 Summary of the Rules for Surface Reaction Data
Rule
9
Description
Three Arrhenius coefficients must appear in order ( A i , i , and E i ) on each Reaction line, separated from each other and from the reaction description by at least one blank space; no blanks are allowed within a number.
10 11
There cannot be more than six reactants or six products in a reaction. To specify a sticking coefficient rather than a rate constant the three numbers after the reaction description have the meaning a i , b i , and c i (see Equation B-59) and the auxiliary information word STICK must appear on the next line of input. To use this option the reaction must have only one gas-phase species as a reactant and its stoichiometric coefficient must be 1.
12
All characters on a line following an exclamation mark are considered comments and are ignored.
A.3.5.3
Surface Reaction Auxiliary Data

Auxiliary information data appears on one or more separate lines after the reaction data line is read, and serves to modify or give additional parameters needed to evaluate that reaction's rate expression. The format in an auxiliary information line is a character string keyword followed by a slash-delimited (/) field containing an appropriate number of parameters (either integer, floating point, E format, or character). Any number of auxiliary information lines may follow a reaction line, in any order, and any number of keywords may appear on an auxiliary information line; however, an auxiliary keyword and its parameter(s) must appear on the same line. Examples of the auxiliary information are shown in Figure A-9. The rules are summarized in Table A-11.
A.3.5.3.1
Reverse Reaction Parameters For a reversible reaction, auxiliary information data may follow the reaction to specify Arrhenius parameters for the reverse-rate expression. Here, the three Arrhenius parameters ( A i , i , and E i ) for the reverse rate must follow the auxiliary keyword REV. Using this option overrides the reverse rates that would normally be computed through the equilibrium constant, Equation B-48. Duplicate Reactions It sometimes happens that two or more reactions can involve the same set of reactants and products, but proceed through distinctly different reaction channels. In these cases it may be appropriate to state a reaction mechanism that has two or more reactions with identical reactants and products, but have different rate parameters. However, duplicate reactions are normally considered errors by the SURFACE KINETICS
A.3.5.3.2
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Pre-processor; if the user requires duplication (e.g., the same reactants and products with different Arrhenius parameters), an auxiliary information statement containing the auxiliary keyword DUP (with no parameters) must follow the reaction line of each duplicate reaction (including the first occurrence of the reaction that is duplicated.) For example, to specify different rate expressions for each of three identical reactions, there must be three occurrences of the keyword DUP, one following each of the reactions. A.3.5.3.3 Sticking Coefficients If the three coefficients given in the second field of the reaction line are to be interpreted as the parameters a i , b i , and c i of Equation B-59 for a sticking coefficient, then the keyword STICK (with no parameters) must follow the reaction line as auxiliary information. There can be only one gas-phase reactant species in a sticking-coefficient reaction; moreover, its stoichiometric coefficient must be 1. Motz-Wise Correction By default the Motz-Wise9 (p. 63) correction of Equation B-61 will not be applied to any reactions using sticking coefficients unless the MWON keyword is given on the REACTIONS line (discussed earlier), in which the new default will be to apply this term. Whichever of these choices has been set as the default can be overridden for an individual sticking-coefficient reaction by including the auxiliary keyword MWOFF or MWON following the reaction line. Arbitrary Reaction Orders The reaction order, i.e., the dependence of the reaction's rate-of-progress upon the concentration of chemical species, can be changed via the FORD or RORD auxiliary keywords for the forward or reverse reaction, respectively. Each occurrence of these keywords must be followed by the species name and the new reaction order, e.g., FORD/SI(S) 0.5/. This option overrides the values of ' ki and '' ki in Equation B-44 pertaining to the particular species named on the line. The reaction order for all other species maintain their default values of ' ki and '' ki . Multiple occurrences of the FORD and RORD construct may appear on the auxiliary line. A FORD or RORD keyword can be specified even for species that do not appear as a reactant or product in the reaction, although one might reasonably wonder how such a functional dependence could occur. Coverage Dependent Reactions To modify the expression for the forward rate constant by optional coverage parameters (see Equation B-56) one uses the auxiliary keyword COV followed by (slash delimited) surface species name and the three parameters ki , ki and ki . More than one set of COV data can appear for a given reaction, and these would be applied multiplicatively as in Equation B-56.
A.3.5.3.4
A.3.5.3.5
A.3.5.3.6
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A.3.5.3.7
Unit Specifications for Reaction Parameters The default units for specifying the reaction rate parameters (either the global defaults set-up by the SURFACE KINETICS Pre-processor, or the set of units requested by the user on the REACTION line) can be overridden for an individual reaction through use of the UNITS auxiliary keyword. Following the reaction, one activates this option with UNITS/string/, where string is one of the unit specifiers EVOLTS, KELVINS, CAL/MOLE, KCAL/MOLE, JOULES/MOLE, or KJOULES/MOLE (to change the units for parameters that have energy units), or MOLES or MOLECULES (to change the units of the pre-exponential A i ). The UNITS auxiliary keyword allows only one string parameter, but the user can repeat the UNITS/string/ option as many times as needed for a given reaction.
Even if the default energy units are changed by giving one of the UNITS keyword, the temperature appearing in the Arrhenius expression of Equation B-47, i.e., in T raised to the
power and in the denominator of the activation energy term, is still in Kelvins.
A.3.5.3.8
Langmuir Hinshelwood and Eley-Rideal Reaction Parameters In the case of a Langmuir-Hinshelwood reaction, the numbers on the primary reaction description line give A , and E a for the rate constant. By default, the equilibrium constants in the numerator are included in the rate constant ( k in Equation B-65 is used, see Section B.2.4.5). The default stoichiometric coefficients for the chemical species concentrations in the numerator can be overridden using the FORD keyword. The units of the rate parameters should follow those used in the reaction mechanism description as a whole, either the default moles, cm, and sec, or whatever is declared in the REACTIONS line. The dimensions of the rate constant need to be matched to the order of the reaction, either the default from the law of mass-action, or whatever has been specified via FORD statements. The auxiliary keyword, LANG, on a supplementary line, indicates the use of the Langmuir-Hinshelwood rate expression. It can only be used for an irreversible reaction, and one auxiliary line should be supplied for each species appearing in the denominator of Equation B-65. The keyword is followed, in slash delimited format, by the species name, the pre-exponential, temperature factor, and enthalpy for the equilibrium constant, and the reaction order for that species (usually one). The equilibrium constant is defined as K = AT exp ( H RT ) , in parallel with the standard expression for rate constants.
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An additional auxiliary keyword, LHDE, allows the default value of 2 for the overall exponent for the denominator ( m ) to be overridden. To specify an Eley-Rideal reaction, this keyword would be used to set m to 1. The use of any positive number is permitted, including real or fractional numbers. The auxiliary keyword LHNU allows the explicit inclusion of equilibrium constants in the numerator the LH rate expression (the use of use k rather than k , see Section B.2.4.5). This keyword is followed by a slash delimited list of species names. For each species in the list, a multiplier of K will be applied to the rate constant. Each species listed in a LHNU statement must have a LANG statement. In the rare case that the desired rate expression does not have matching values for l i and n i (see Equation B-65) for a given species, the LHNU option should not be used because the units will not be correct. In such cases, the user should manually lump the K values with k to yield k . If LANG is used with a complete set of LHNU statements, the rate constant should be provided by the user in moles cm-2sec-1, or whatever units have been specified on the REACTIONS line. An additional auxiliary keyword LHPR indicates that the equilibrium constants are given in pressure units. The keyword will affect the equilibrium constants for the specified reaction only; the reaction rate will remain in whatever units are given on the REACTION line, or in moles, cm, and sec. The keyword is followed by the name of the pressure unit being used: atm, bar, torr, pasc (for Pascals), or dyne (for dynes per square cm), where the names are not case sensitive. A.3.5.3.9 Optional User Rate Subroutine SKUPROG The auxiliary keyword USRPROG, optionally appended by a slash(/)-delimited integer parameter, implies that the net rate-of-progress for the reaction will be obtained by calling a user-supplied subroutine, SKUPROG. The optional parameter allows the user to select from more than one type of rate formulation. Wherever the net reaction rate is required, it will be obtained by calling the user-written subroutine. USRPROG applies only to irreversible reactions, and cannot be used in conjunction with USRPROD (entered on the REACTIONS line). A template of SKUPROD can be obtained from Reaction Design as well as information on how to compile and link user routines into FLUENT/CHEMKINCFD. Summary of Surface Auxiliary Reaction Data Any number of auxiliary information lines may follow a reaction line, in any order, and any number of keywords may appear on an auxiliary information line; however, an auxiliary keyword and its parameter(s) must appear on the same line. The above rules are summarized in Table A-12. Examples of auxiliary information are shown in Figure A-9.
A.3.5.3.10
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Table A-12 Summary of the Rules for Surface Auxiliary Data
Rule
1
Description
Auxiliary information lines may follow a reversible reaction to specify the reverse rate parameters explicitly; auxiliary information must follow any reactions that are duplicated.
2 3
Auxiliary keyword declarations may appear anywhere on the line, in any order. Any number of auxiliary keywords may appear on a line, and more than one line may be used, but a keyword and its parameter(s) must appear on the same line.
Multiple keywords appearing on the same line must be separated by at least one blank space.
Any blank spaces between a keyword and the first slash are ignored and any blanks between the slashes and parameter(s) are also ignored. However, no blank spaces are allowed within a keyword or parameter.
The keyword REV followed by three slash-delimited Arrhenius coefficients may be used to specify the reverse rate parameters.
The auxiliary keyword DUPLICATE (or DUP) must follow every occurrence of a duplicated reaction.
The keyword STICK indicates that the three coefficients on the reaction line are to be interpreted as the parameters a i , b i , and c i in Equation B-59. There must be exactly one gas-phase reactant species; its stoichiometric coefficient must be 1.
The keyword COV is used to modify the forward rate constant by the expression in Equation B-56. The word COV is followed by a surface species name and the three coverage parameters ki , ki and ki . The four entries after the word COV are slash-delimited.
10
The FORD or RORD auxiliary keywords can be used to change the reaction order (with respect to species concentration) of the forward or reverse reaction, respectively, for any species in the mechanism, regardless of whether the species appears as a reactant or a product in the reaction. The species name and the new reaction order (slash-delimited) follow the keyword.
11
The UNITS auxiliary keyword can be used to override the current default units for parameters with energy units or the pre-exponential for a given reaction. The usage is UNITS/string/, where string is one of the following: EVOLTS,
KELVINS, CAL/MOLE, KCAL/MOLE, JOULES/MOLE, or KJOULES/MOLE (for
parameters with energy units), or MOLES or MOLECULES (for pre-exponential).
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Table A-12 Summary of the Rules for Surface Auxiliary Data
Rule
12
Description
The string MWOFF can be used to turn off the Motz-Wise9 (p. 63) correction of
Equation B-61 or the string MWON can be used to turn on this correction for a
sticking coefficient reaction. Using the MWOFF or MWON auxiliary keyword overrides the default option set up on the REACTION line or the default supplied by SURFACE KINETICS Pre-processor (which is MWON). 13 All characters on a line following an exclamation mark are considered comments and are ignored. 14 The LANG keyword can be used to input a Langmuir-Hinshelwood rate expression. The keyword is followed by a species name, three parameters giving the equilibrium constant, and a fourth parameter giving the order of that species in the reaction. Additional auxiliary keywords LHDE, LHNU, and LHPR provide more flexibility in the form of the Langmuir-Hinshelwood or Eley-Rideal rate expressions.
Figure A-9 Examples of Auxiliary Surface Reaction Data
! THE FOLLOWING ARE *CONTRIVED* EXAMPLES OF AUXILIARY KEYWORD USAGE

SICL(S) <=> CL + SI(S) 1.0E-3 0.0 2. REV/1.0E13 0.0 37./ 0.1 1.1 20.
CL + SICL(S) <=> CL2 + SI(S) DUPLICATE STICK RORD /SI(S) 0/ CL + SICL(S) <=> CL2 + SI(S) DUPLICATE COV/SICL(S) -1.2 0.5 32./ CL* => CL STICK MWOFF E + CL+ + SICL3(S) + SI(B) => SICL4 + SI(S) BOHM ENRGDEP/1. 0.5 1.0/ UNITS/EVOLT/ E + CL+ + #SICL3(S) + #SI(B) + SICL(S) & => SICL2(S) + #SICL2 + #SICL(S) BOHM YIELD/0.0712 1.21 0.5 1.0/ UNITS/EVOLT/ E + CL2+ + SICL3(S) + SI(B) => SICL4 + SICL(S) FORD/ CL2+ 2.43/ A + B => C + D 7.9E13 0. LANG /A 3.6308E+36 0.0 -7.36 2./ LHDE /2/ LHNU /A C/ LHNU /A A/ LHPR /atm/
1.4E11 0.0 FORD/CL+ 1.0/ 1.0 0.0 0.50 0.0
15. 0. 0.
0.50
0.0
0.0
0.50 56000.
0.0
0.0
A.3.5.4
Unit Conversion for Pre-exponential Factor

The Pre-processor provides the option of specifying units of the Arrhenius parameters. The parameters are always stored internally in the same way, i.e., activation energies in Kelvins, dimensionless temperature exponents, and preexponential factors consistent with cm, molecules, sec and K. The program converts the user input activation energies accordingly.
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However, it is worthwhile to state explicitly the conversion for the Arrhenius preexponential constant. In converting from molecules to moles
Equation A-4
A i ( moles ) = A i ( molecules ) ( N A )
n1
where N A is the Avogadro number, and

Equation A-5 K s(N s)
l l
n =
k=1
' ki
Note that the ' ki are the stoichiometric coefficients for the gas-phase and surface reactant species (not product species or bulk-phase species).
A.3.6
Error Checks
The SURFACE KINETICS Pre-processor checks each input line for proper syntax and writes diagnostic messages if errors are encountered. The input must be error free before FLUENT/CHEMKIN-CFD may be run. Possibilities for an error condition are as follows:
Data Type
Site and Bulk Species Data
Possible Errors
A duplicated species symbol (name) is not considered a fatal error, but is eliminated from consideration and a warning diagnostic message is printed. No site density is found for a declared site, or the site density is negative. No thermodynamic data are found for a declared species. A site or bulk phase name duplicates another phase name (gas surface site, or bulk phase name). A phase or species name contains an illegal character. Site occupancy number is negative. Bulk density for a bulk species is negative.
Thermodynamic Data
Thermodynamic data are format sensitive and therefore provide possibilities for error if not formatted exactly as described by Table A-1.
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Data Type
Possible Errors
An element in the thermodynamic data for a declared species is not included in the GAS-PHASE KINETICS Pre-processor input element data. With the THERMO ALL option, line 2 (of Table A-1) is not found.
Reaction Data
A delimiter =>, <=>, or = between the reactants and the products is not found. Three Arrhenius parameters are not found. Reactants and/or products species names are not properly delineated by a plus sign (+). A species listed as a reactant or product is not declared in the species data. A reaction does not satisfy elemental balance. The number of sites in a reaction does not balance and the word
NONCON was not included on the first REACTIONS line.
The charge of the reaction does not balance. A reaction is a duplicate not declared by the auxiliary data keyword
DUP.
There are more than six reactants or six products in a reaction. Auxiliary Reaction Data An unknown or misspelled keyword occurs. Parameters for a keyword are not enclosed in slashes. There are the wrong number of parameters for a keyword.
REV is declared for an irreversible reaction.
Pre-exponential factor for a sticking coefficient is negative. For a sticking-coefficient reaction, there is more than one gasphase species, or the stoichiometric coefficient for the gas-phase species is not 1. The electron species was not declared in the list of species in the GAS-PHASE KINETICS input when ionic species are present. Invalid string given with the UNITS auxiliary keyword. Invalid species name given for FORD or RORD auxiliary keywords. A reaction order value was not found with the FORD or RORD keyword.
RORD given for an irreversible reactions.
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Data Type
Possible Errors
LANG is declared for a reversible reaction, or for the same reaction
as STICK or COV.
USRPROG given for a USRPROD mechanism. USRPROG given for a reversible reaction.
A.3.7
Mechanisms with Multiple Materials

In some reacting flow simulations there may be different types of solid surfaces at which very distinct heterogeneous chemistry takes place. For example, in a plasma etching reactor there might be a wafer composed of silicon and reactor side-walls composed of aluminum. Although the main purpose of the simulation might be to understand the etching chemistry at the wafer, reactions at the walls also serve to create and destroy species. Because chemical reaction mechanisms occurring at the surfaces can be quite different, Pre-processor allows the use of multiple materials in input files. This essentially allows the user to specify several different and complete surface reaction mechanisms, one after another (separated by a MATERIAL line). An example of such a SURFACE KINETICS input file is shown in Figure A-10.
The mechanism has been contrived to illustrate a variety of points about the data structures and should not be taken as a source of data for silicon or aluminum processes.
Figure A-10
Surface Kinetics Input File using Multiple Materials

!----------Surface Kinetics Pre-processor Input---------------MATERIAL WAFER SITE/POLY/ SDEN/2.25e-9/ SI(S) SICL(S) SICL2(S) SICL3(S) END BULK SI(B)/2.33/ END REACTIONS MWOFF CL + SI(S) => SICL(S) 1.0 0.0 0.0 STICK CL + SICL(S) => SICL2(S) 0.4 0.0 0.0 STICK CL + SICL2(S) => SICL3(S) 0.1 0.0 0.0 STICK END MATERIAL WALL SITE/METAL/ SDEN/2.25E-9/ AL(S) ALCL(S) ALCL2(S) END BULK AL(B)/2.7/ END REACTIONS MWOFF CL + AL(S) => ALCL(S) 1.0 0.0 0.0 STICK CL + ALCL(S) => ALCL2(S) 0.4 0.0 0.0 STICK CL + ALCL2(S) + AL(B) => ALCL3 + AL(S) 0.1 0.0 0.0 STICK END
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A.4
TRANSPORT Input
For chemistry mechanisms where CHEMKIN transport data has been specified, FLUENT will use this data to generate molecular transport properties for multicomponent mixtures.
It is important to note here that although FLUENT will access a CHEMKIN-compatible transportproperty database (e.g., tran.dat), the formulas used to calculate molecular diffusion, thermal conductivity, or viscosity may be different than those used in CHEMKIN software. Users should refer to FLUENT documentation for details on the formulations employed by FLUENT. The format of the transport-property input data described here, however, is identical to the description in the CHEMKIN Input Manual, Chapter 5.
In this section, we describe the parameters included in a CHEMKIN-compatible transport data file. Such a data file should contain molecular parameters for all of the gas-phase species defined in the system of interest. For each species, the parameters that must be included are: the Lennard-Jones well depth k B in Kelvins, the Lennard-Jones collision diameter in Angstroms, the dipole moment in Debyes, the polarizability in cubic Angstroms, the rotational relaxation collision number, Z rot. (unitless) and an indicator regarding the nature and geometrical configuration of the molecule. Species names must correspond exactly to those defined in the GAS-PHASE KINETICS input file and in the Thermodynamic Database file. Table A-14 provides examples of TRANSPORT input data. The first 16 columns in each line of the database are reserved for the species name. Columns 17 through 80 are free-format, and they contain the molecular parameters for each species. The parameters are, in order: 1. An index indicating whether the molecule has a monatomic, linear or nonlinear geometrical configuration. If the index is 0, the molecule is a single atom. If the index is 1 the molecule is linear, and if it is 2, the molecule is nonlinear. 2. The Lennard-Jones potential well depth k B in Kelvins. 3. The Lennard-Jones collision diameter in Angstroms. 4. The dipole moment in Debye.
A Debye is 10-18cm3/2erg1/2.
5. The polarizability in cubic Angstroms.
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6. The rotational relaxation collision number Z rot. at 298K. 7. A comment line is one that has either a period (.), slash (/), or exclamation mark (!) as the first non-blank character. In addition, on any line, any input that follows an exclamation mark is taken as a comment.
Table A-14 Example Entries in a Transport Data file
Species Name Al2Me6 AlMe3 AR AR* Geometry 2 2 0 0
kB
471. 471. 136.500 136.500
6.71 5.30 3.330 3.330
0.0 0.0 0.000 0.000
0.0 0.0 0.000 0.000
Z rot.
1.0 1.0 0.000 0.000
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Theoretical Background
This chapter provides a description of some of the underlying formulations and equations behind the calculations performed by CHEMKIN-CFD routines that provide net rates of production of species in the gas-phase and net rates of production of species at gas/surface interfaces, as well as thermodynamic properties, to the CHEMKIN-CFD module. Based on CHEMKIN, the CHEMKIN-CFD module offers a broad range of options and flexibility in describing chemical kinetic input.
At this time, the transport property calculations are performed by FLUENT using FLUENTs own formulations rather than CHEMKIN-based approaches.
B.1
Gas-phase Reaction Rate Formulations

Consider elementary reversible (or irreversible) reactions involving K chemical species that can be represented in the general form
Equation B-1 K K
ki k ki k
k=1 k=1
( i = 1 ,, I )
The stoichiometric coefficients ki are integer numbers and k is the chemical symbol for the k th species. The superscript indicates forward stoichiometric coefficients, while indicates reverse stoichiometric coefficients. Normally, an elementary reaction involves only three or four species; hence the ki matrix is quite sparse for a large set of reactions. For non-elementary reactions, Equation B-1 also represents the reaction expression, but the stoichiometric coefficients may be nonintegers.
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May 2009
Chapter B: Theoretical Background
The production rate k of the k th species can be written as a summation of the rateof-progress variables for all reactions involving the k th species
Equation B-2 I
k =
where
Equation B-3
ki qi
i=1
( k = 1 ,, K )
ki = ki ki
The rate of progress variable q i for the i th reaction is given by the difference of the forward and reverse rates as
Equation B-4 K
q i = k fi [ X k ]
k=1
ki
k ri [ X k ]
k=1
ki
where [ X k ] is the molar concentration of the k th species and k fi and k ri are the forward and reverse rate constants of the i th reaction. As indicated in Equation B-4, the rate-of-progress of a reaction is evaluated, by default, using the concentration of each reactant or product species raised to the power of its stoichiometric coefficient. Thus, the rate-of-progress of a reaction that includes species A with a coefficient of 2 will be second-order with respect to the concentration of A . Equation B-4 is always valid when mass-action kinetics are obeyed, and when the mechanism is written in terms of elementary reactions. The user has the option to define an arbitrary reaction order for a species in a reaction in place of the coefficients used in Equation B-4. This option is described further below. The forward rate constants for the I reactions are generally assumed to have the following Arrhenius temperature dependence:
Equation B-5
Ei k fi = A i T i exp ------- R c T
where the pre-exponential factor A i , the temperature exponent i , and the activation energy E i are specified. These three parameters are required input for each reaction.
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Two gas constants, R and R c are used throughout this chapter. R c is used only in conjunction with the activation energy E i and has compatible units. The reason for the duality is that many users would rather use units of cal/mole for the activation energies even though erg/mole are used elsewhere.
In thermal systems, the reverse rate constants k ri are related to the forward rate constants through the equilibrium constants by
Equation B-6
k fi k ri = -----K ci
Although K ci is given in concentration units, the equilibrium constants are more easily determined from the thermodynamic properties in pressure units; they are related by
Equation B-7
K
K ci
P atm k = 1 = K pi -------- RT
ki
The equilibrium constants K pi are obtained with the relationship

Equation B-8
K pi
Si Hi - ---------- = exp -------RT R
B.1.1
Arbitrary Reaction Order

Often in real-world applications the elementary kinetics are not known. In some cases, an experimental measurement finds that the rate of reaction is proportional to the concentration of a species raised to a some arbitrary power (different from its stoichiometric coefficient). The user may declare that the rate-of-progress of a reaction is proportional to the concentration of any species (regardless of whether that species even appears as a reactant or a product in the reaction) raised to any specified power. To modify the reaction order for the reaction in the forward or reverse direction, the user must declare the FORD or RORD auxiliary keywords, respectively, in the GAS-PHASE KINETICS input file. (These keywords are discussed in Section A.2.4.3.7.)
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When the reaction-order-dependence of reaction i is changed via the FORD or RORD keywords, the rate-of-progress variable q i for the reaction is evaluated by:
Equation B-9 K K F ki
q i = k fi [ X k ]
k=1
k ri [ X k ]
k=1
R ki
where F ki is the reaction order specified through the FORD keyword and R ki is the reaction order specified through the RORD keyword for species k . The default for species participating in reaction i is the normal mass-action kinetics values:
Equation B-10
F ki = ki
and
Equation B-11
R ki = ki
if an order-change parameter is not given for species k . The user should exercise caution when specifying a change of reaction order, as such a change may produce unexpected and unphysical results in a kinetic simulation. For example, the user should consider the kinetics of the reverse reaction when changing reaction-orders for the forward reaction. Such a reaction may no longer satisfy microscopic reversibility. In such cases, it may be advisable to specify that the reaction is irreversible.
B.1.2
Three-Body Reactions
In some reactions a third body is required for the reaction to proceed; this is often the case in dissociation or recombination reactions, such as H + O2 + M HO2 +M When a third body is needed, the concentration of the effective third body must appear in the expression for the rate-of-progress variable. Accordingly, the rate-ofprogress variable is different from Equation B-4 by the first factor in the equation:
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Equation B-12 K K K ki ki q i = ( a ki ) [ X k ] k fi [ X k ] k ri [ X k ] k = 1 k = 1 k=1
If all species in the mixture contribute equally as third bodies, then a ki = 1 for all k , and the first factor is the total concentration of the mixture,
Equation B-13 K
[M] =
[ Xk ]
k=1
However, it is often the case that some species act more efficiently as third bodies than do others. The a ki that differ from 1 must be specified by input, as described in Section A.2.4.3.1.
B.1.3
Pressure-Dependent Reactions
Under certain conditions, some reaction rate expressions depend on pressure as well as temperature. CHEMKIN-CFD, LIKE CHEMKIN, provides for several kinds of pressuredependent reaction-rate formulations. These include unimolecular/recombination falloff reactions, chemically activated bimolecular reactions (where reaction rates typically decrease with increasing pressure), multi-well, multi-channel reactions using Chebyshev polynomials, and logarithmic interpolation based on reaction rates at discrete pressures. For both the unimolecular/recombination fall-off reactions and the chemically activated bimolecular reactions, the user may choose from several optional expressions that blend smoothly between high- and low-pressure limiting rate expressions. The multi-channel and logarithmic-interpolation reaction descriptions allow very general fitting to capture complex pressure dependence.
B.1.3.1
Unimolecular/Recombination Fall-off Reactions

As an example of a unimolecular/recombination fall-off reaction, consider methyl recombination. In the high-pressure limit, the appropriate description of the reaction is CH3 + CH3 C2H6 + M. In the low-pressure limit, a third-body collision is required to provide the energy necessary for the reaction to proceed, i.e., the appropriate description is CH3 + CH3+ M C2H6 + M. When such a reaction is at either limit, the (solely temperature-dependent) rate expressions discussed in the preceding
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paragraphs are applicable. However, when the pressure and temperature are such that the reaction is between the limits, the rate expressions are more complicated. To denote a reaction that is in this fall-off region, we write the reaction with the positive +M enclosed in parentheses, CH3 + CH3(+M) C2H6(+M). There are several methods of representing the rate expressions in this fall-off region. The simplest one is due to Lindemann.10 There are also now two other (and related) methods that provide a more accurate description of the fall-off region than does the simple Lindemann form. We provide three of these forms as options. For the Lindemann form, Arrhenius rate parameters are required for both the highand low-pressure limiting cases, and these are blended to produce a pressuredependent rate expression. In Arrhenius form, the parameters are given for the highpressure limit k and the low-pressure limit k 0 as follows:
Equation B-14
k 0 = A 0 T exp ( E 0 R c T )
Equation B-15
k = A T
exp ( E R c T )
The rate constant at any pressure is then taken to be

Equation B-16
Pr - F k = k ------------- 1 + P r
where the reduced pressure P r is given by
Equation B-17
k0 [ M ] P r = -------------k
and [ M ] is the concentration of the mixture, possibly including enhanced third-body efficiencies. For this example, note that the units for k are 1/sec, k 0 are cm3/(mole sec), and k are 1 sec . If the F in Equation B-16 is unity, then this is the Lindemann form. The other descriptions involve more complex expressions for the function F . In the Troe form,11 F is given by
10.F. Lindemann, Trans. Faraday Soc.17:598 (1922).
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Equation B-18
log P r + c log F = 1 + --------------------------------------n d ( log P r + c )
2 1
log F cent
The constants in Equation B-18 are

Equation B-19
c = 0.4 0.67 log F cent

Equation B-20
n = 0.75 1.27 log F cent

Equation B-21
d = 0.14
and
Equation B-22
F cent = ( 1 ) exp ( T T
***
) + exp ( T T ) + exp ( T
* **
**
T)
The four parameters , T , T , and T must be specified as auxiliary input, as ** described in Section A.2.4.3.2. It is often the case that the parameter T is not used. For this reason, the use of either three or four parameters is allowed. The approach taken at SRI International by Stewart, et al.12 is in many ways similar to that taken by Troe, but the blending function F is approximated differently. Here, F is given by
Equation B-23
***
b T - + exp ----- F = d a exp ---- T c

where
Equation B-24
X e
1 X = -----------------------2 1 + log P r
11.R. G. Gilbert, K. Luther, and J. Troe, Ber. Bunsenges. Phys. Chem. 87:169 (1983). 12.P. H. Stewart, C. W. Larson, and D. M. Golden, Combustion and Flame 75:25 (1989).
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In addition to the six Arrhenius parametersthree each for the low-pressure limit k 0 and high-pressure limit k expressionsthe user must supply the parameters a , b , and c in the F expression. The parameters d and e were not discussed by Stewart, et al., but we have included them as additional optional parameters to increase flexibility. If one wishes, d and e can be considered parameters that define a weakcollision efficiency factor, in the event that one wants to compute strong-collision rate parameters and correct them with such a factor.
B.1.3.2
Chemically Activated Bimolecular Reactions

As an example of a chemically activated bimolecular reaction, consider the reaction CH3 + CH3(+M) C2H5 + H(+M). This reaction, which is endothermic, occurs through the same chemically activated C2H6* adduct as does the recombination reaction CH3 + CH3(+M) C2H6 (+M). As the pressure increases, deactivating collisions of C2H6* with other molecules cause the rate coefficient for C2H6 formation to increase. At the same time, these deactivating collisions preclude the dissociation of C2H6* into C2H5 + H, thus causing this rate coefficient to decrease with increasing pressure. We assume the rate coefficient for a chemically activated bimolecular reaction to be described by the following function:
Equation B-25
1 - F k = k 0 ------------- 1 + P r
where 1 ( 1 + P r ) is analogous to the Lindemann form of Equation B-16. Note that in Equation B-25, k 0 is the pressure-independent factor, whereas in Equation B-16 it is k . The three choices for the F function are exactly the same as for the unimolecular fall-off reactions, i.e., the Lindemann ( F = 1 ), Troe, or SRI forms.
B.1.3.3
General Pressure Dependence Using Logarithmic Interpolation

Miller and Lutz13 recently developed a generalized method for describing the pressure dependence of a reaction rate based on direct interpolation of reaction rates specified at individual pressures. In this formulation, the reaction rate is described in terms of the standard modified Arrhenius rate parameters. Different rate parameters are given for discrete pressures within the pressure range of interest. When the actual reaction rate is computed, the rate parameters will be determined through logarithmic interpolation of the specified rate constants, at the current pressure from the simulation. This approach provides a very straight-forward way for users to include rate data from more than one pressure regime.
13.J. A. Miller and A. E. Lutz, personal communication, August 2003.
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For a given reaction, then, the user would supply rate parameters j k ( T, P j ) = A j T exp ( E j R c T ) for a set of P j pressures. The set of pressure points for which rate parameters are specified must include at least two different pressures. If the rate at a given pressure cannot be described by a single set of Arrhenius parameters, more than one set may be provided. In such cases, the reaction rates will be treated in a similar manner as for DUPLICATE reactions, meaning that CHEMKIN will use the sum of the sets of rates provided for the given pressure at that point. During a simulation, if the current pressure is within 1% of one of the pressures for which rate constants were provided, then that set of rate parameters will be used directly. However, If the current pressure is in between the pressure points provided, then the rate will be obtained by a linear interpolation of log k as a function of log P (natural logarithms). For P between P i and P i + i, k , k is obtained using Equation B-26.
Equation B-26
log P log P i log k = log k i + ( log k i + l log k i ) ------------------------------------log P i + l log P i

If the rate of the reaction is desired for a pressure lower than any of those provided, the rate parameters provided for the lowest pressure are used. Likewise, if rate of the reaction is desired for a pressure higher than any of those provided, the rate parameters provided for the highest pressure are used. This logarithmic interpolation method can be used as an alternative approach to describing any type of pressure dependence, including the multiple-well, multiplechannel reactions discussed in Section B.1.3.4. It has the advantage of being conceptually straightforward to implement. However, the resolution or accuracy of the pressure dependence will depend on the number of pressure points included for each reaction.
B.1.3.4
Multiple-well Multiple-channel Reactions Using Chebyshev Polynomials

An example of the multiple-well, multiple-channel chemically activated reaction is the reaction of the ethyl radical with oxygen, C2H5 + O2. This chemically activated reaction occurs through three wells. The initial well corresponds to the chemically activated molecule CH3CH2OO formed by the radical addition process via a loose transition state. This activated molecule can further isomerize to the hydroperoxy radicals CH2CH2OOH and CH2CHOOH leading to different products.14 The Lindemann based methods described in the previous sections, i.e., the Lindemann,
14.P. K. Venkatesh, J Phys. Chem. A 104(2):280-287 (2000).
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Troe, and SRI forms, although accurate for representing the falloff behavior of singlewell reactions, do not apply well to multiple-well reactions.15 A method based on the Chebyshev expansions are proposed by Venkatesh, et al.15 (p. 88) for approximating the pressure and temperature-dependent behavior of multiple-well reactions. The Chebyshev expansions provide accurate approximations over any given temperature and pressure domain for single- and multiple-well reactions. However, these approximates should not be used for extrapolative studies outside their defined domain.
The implementation of pressure-dependent reaction rates through the use of Chebyshev polynomials is based on the work of Jeff Ing, Chad Sheng, and Joseph W. Bozzelli at the New Jersey Institute of Technology.16
Instead of using the modified Arrhenius form for the rate coefficient, the Chebyshev expansions approximate the logarithm of the rate coefficient directly as a truncated bivariate Chebyshev series in the reverse temperature and logarithm of the pressure. Since the Chebyshev polynomials are only defined in the interval of [-1, +1], the temperature and pressure boundaries for the approximation must be established first, i.e.,
T min T T max
and
P min P P max
The T P domain is then mapped onto a square bounded by 1 using the transformations
Equation B-27
2 T T min T max = -------------------------------------------T 1 1 T min T max

and
15.P. K. Venkatesh, A.Y. Chang, A.M. Dean, M. H. Cohen and R.W. Carr, J. AIChE 43:1331-1340 (1997). 16.Jeff Ing, Chad Sheng, and Joseph W. Bozzelli, personal communication, 2002.
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Equation B-28
log P log P min log P max = 2 ----------------------------------------------------------------P log P max log P min
The logarithm of the rate coefficient is approximated by the Chebyshev expansions as
Equation B-29 N M
,P ) log k (T

n = 1m = 1
) (P ) a nm n ( T m
where the Chebyshev polynomials of the first kind of degree n 1 are given by
Equation B-30
( x ) = cos ( ( n 1 ) cos ( x ) )
n = 1, 2,
with 1 x +1 . The integers N and M denote the number of basis functions along the temperature and the pressure axis, respectively. The accuracy of the approximates will increase monotonically with N and M . The N M coefficients, a nm , of the Chebyshev expansions are determined from a least-squares fit to a set of ,P ) , computed from a detailed theory such as the Ricerate coefficient data points, k (T Ramsperger-Kassel-Marcus (RRKM) theory. To ensure the approximation is uniform over the desired domain, the computed rate coefficient data must be on the GaussChebyshev grid. For example, if the computed rate coefficient data is on a Gauss and P , must be the roots of a high-order Chebyshev grid, its coordinates, T i j Chebyshev polynomial of the first kind given by
Equation B-31
i1 = cos 2 ------------- T i 2 dT
Equation B-32
j1 = cos 2 ------------- P j 2 dP
where 1 i d T and 1 j d P . The integers d T and d P are the resolutions of the computed rate coefficient data in the temperature and the pressure direction, respectively. As a necessary condition, the number of basis functions in each direction of the Chebyshev expansions should be no greater than the data resolution of that direction, i.e., N d T and M d P .
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To use the Chebyshev expansions to represent the rate coefficient of a reaction, the user should provide the temperature and pressure limits of the expansion, T max , T min , (auxiliary keyword TCHEB) and P max , P min (auxiliary keyword PCHEB) the number of basis functions used in each direction, N and M , and the N M coefficients, a nm , (auxiliary keyword CHEB). See Section A.2.4.3.3 and Figure A-5 for more information about the use of these keywords.
B.1.4
Landau-Teller Formulation of the Rate Expressions

For reactions such as vibrational energy transfer processes, the Arrhenius form of the rate expression Equation B-5 is often not used. Instead, it is common to use the Landau-Teller expression,
Equation B-33
Ci Bi - + ---------- k fi = A i exp --------- T 1 3 T 2 3

In addition, we have provided the possibility to blend the Arrhenius expression with the Landau-Teller expression in the general expression, as follows:
Equation B-34
Bi Ci Ei - + ---------- + ---------- k fi = A i T i exp ------- R c T T 1 3 T 2 3

Clearly, by setting B i and C i to zero, the Arrhenius expression is recovered, and by setting i and E i to zero, the standard Landau-Teller expression is recovered. If appropriate, however, all the parameters can be used together to provide more flexibility in the reaction-rate expression than could be afforded by one of the forms alone.
B.2
Surface Reaction Rate Formulations

Heterogeneous reaction at the interface between a solid surface and adjacent gas is central to many chemical processes such as chemical vapor deposition, chemical etching, combustion of solids, and catalytic processes. The CHEMKIN-CFD software provides a powerful capability to help model, understand, and optimize important industrial and research chemical processes. The software is based on a systematic convention to translate heterogeneous reaction ideas into a form that is amenable to efficient computation.
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The first part of this section is a discussion of how to formulate a surface reaction mechanism. This is followed by a compendium of some important equations in heterogeneous chemical kinetics. Many of the equations are simply definitions. Then we discuss how to set up the required symbolic input to define a surface reaction mechanism. We have allowed the possibility of including multiple site types, multiple mixtures of bulk species, and multiple materials. Each site type and bulk mixture may contain several species. Therefore, the data structures needed to refer to the phases and the species can be complex.
B.2.1
Development of a Surface Formalism

In this section we discuss the mathematical formalism developed to describe surface kinetics for events such as adsorption, desorption, surface reactions, and deposition. This formalism is essentially a set of rules for keeping track of surface species concentrations, conservation of mass and surface sites, mass-action kinetics, and rates (such as deposition or etching rates). For this discussion we define three types of species: gas-phase, surface, and bulk. The first is a species in the gas phase above the surface, which might be denoted in a reaction by (g). A surface species, perhaps denoted by (s), is defined to be the chemical species on the top-most layer of the solid, i.e., at the solid-gas interface.
In actuality there is no constraint that the surface must be only one atom thick. However, defining a surface that is several monolayers thick may be conceptually much more difficult to deal with.
Each surface species occupies one or more sites; the total number of sites is often assumed to be conserved. Any species in the solid below the surface layer is defined to be a bulk species and might be denoted by (b). In writing elementary reactions for a surface mechanism in a kinetic model, mass, elemental composition, and charge must all be conserved. There can be more than one type of site on the surface. For example, one could specify that a surface consists of ledge sites and plane sites. The number of sites of each type might be a characteristic of the crystal face. In our formalism there can be any number of site types. One may define a species that only resides on a certain type of site. For example, the thermodynamic properties of a hydrogen atom on a ledge site might be different from a hydrogen on a plane site, and they could be
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specified as different species (even though their elemental composition is the same). The population of different species occupying a given type of site is specified by site fractions. The sum of the site fractions of the species on a given site is 1. (Thus an open site'' is considered as a distinct species.) In the bulk there can be different types of bulk species. The simplest consists of a pure species. There can be any number of pure bulk species. It is also possible to specify a bulk mixture with components A and B. The composition of the bulk phase may be input by the user by specifying the activities of each of the bulk-phase components. The activity of a bulk species is defined in terms of the following equation for the chemical potential:
Equation B-35
k ( T, P, X ) = k ( T ) + RT ln ( a k ( T, P, X ) )
where k is the standard state chemical potential of species k at temperature T and at the standard pressure, 1 atm. The vector X represents an array of the mole fractions of the species. Two conventions are normally used to complete the specification of the activity coefficient: 1. If the standard state is defined as a pure bulk phase of k at temperature T and 1 atm, then a k is further defined to approach X k as X k approaches 1 at 1 atm (Raoult's Law). 2. If the standard state is defined as the hypothetical state of species k in infinite dilution in bulk-phase species j at temperature T and 1 atm, then is further defined to approach X k as X k approaches 0 at 1 atm (Henry's Law). Both conventions for the standard state work with the CHEMKIN-CFD module. The activities of all components of an ideal solution must sum to 1; this condition is enforced by CHEMKIN-CFD. Since the user may define a number of different types of species (gas species, any number of types of surface sites, species residing on surface sites, pure bulk species, bulk mixtures, and species present in a bulk mixture), it is necessary to track them throughout the simulation. We use the notion of different physical phases to group the chemical species in a problem. Our nomenclature corresponds to that of Eriksson,17 which has been extended to account for surface sites. The order in which we discuss the phases is the order in which they are grouped internally in the mechanism data structure.
o
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Phase number 1 is the gas phase. Information about species in the gas phase is extracted from the gas-phase kinetics input. For this phase, the mole fractions of the gas-phase species correspond to species activities, mentioned below. The next phases that may be included in a surface-chemistry mechanism are surface site phases. We consider every type of surface site to be a distinct phase. If there are N s types of sites specified, then phases 2 through N s + 1 are these sites. The user can specify the names of chemical species that exist only on a given site type. The site fractions of all species that can exist on a given type of site (phase) sum to 1. The surface species site fractions also correspond to activities. The last type of phase is a bulk mixture. If a given problem has N b different types of bulk mixtures, then these are considered to be phases N s + 2 through N s + N b + 1 . The user specifies the names of the species that can exist in a given bulk mixture. The amounts of these species are determined indirectly by their activities, which the user supplies. A limiting case is a pure bulk species, which is treated as a bulk mixture with only one chemical species, whose activity is unity if the chemical potential does not depend on pressure. We now consider in more detail how to write chemical reactions involving surface and bulk species. A chemical species on the top layer of the solid, i.e., a surface species, occupies a site. For example, an arsine molecule adsorbed on a surface could occupy a site, and might be denoted AsH3(s). Another example might be a bare gallium atom, Ga(s), on top of a gallium arsenide crystal. What happens if another species, say a gas-phase AsH3, lands on top of the Ga(s) (see Figure B-4)? In this case the gallium atom that was at the surface is covered up, so it is no longer a surface species. In our nomenclature it has become a bulk species. The adsorbed AsH3 now occupies the top-most layer at this site, so it has become the surface species AsH3(s). In our formalism, we would write the adsorption reaction in Figure B-4 as
Figure B-1
Example Reaction for Adsorption, Using Atomic Site Formalism
AsH3(g) + Ga(s) AsH3(s) + Ga(b) In this reaction, the number of sites included on the left-hand side of the reaction equals the number on the right-hand side; the reaction conserves sites. Suppose that we had wanted to describe the reverse reaction, i.e., desorption of AsH3 from the surface. We would then write the reaction as
17.G. Eriksson, Acta Chem. Scand. 25:2651 (1971).
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Figure B-2
Example Reaction for Desorption, Using Atomic Site Formalism
AsH3(s) + Ga(b) AsH3(g) + Ga(s) Here, Ga(b) is included as a reactant in order to achieve site and elemental balance. We denote the formalism described in Figure B-1 and Figure B-2 as the Atomic Site Formalism. An alternate way of posing the above example is to look at the situation on the left side of Figure B-4 not as having a surface gallium atom on a site, but to say that this is really an open site at which some event may take place (see Figure B-5). We would write the reaction of Figure B-5 as
Figure B-3 Example Reaction for Adsorption, Using Open Site Formalism
O(s) + AsH3(g) AsH3(s) where the symbol O(s) was used to denote an open site. Since O(s) contains no elements (it is empty), this reaction conserves both sites and elements. We denote the formalism described in Figure B-3 as the Open Site Formalism. The Atomic Site and Open Site Formalisms are equally valid ways of stating these surface reactions. Either is allowed by the SURFACE KINETICS Pre-processor. Personal preference or, perhaps, the nature of a particular problem might dictate one over the other. Note that an open site must be considered as a species. What are the thermochemical implications of reactions such as Figure B-2 and Figure B-3? In the Atomic Site Formalism, the interpretation is straightforward. In Figure B-2 we have converted AsH3(g) and Ga(s) into AsH3(s) and Ga(b). Thus, the change in a thermochemical property, e.g., H rxn , is just the difference in the heats of formation of the products and the reactants. What about in the Open Site Formalism? What are the properties of O(s), the open site? Because these two formalisms describe an identical physical event, it is evident the properties of the open site must be related to those of Ga(b) and Ga(s). For example, the heat of formation of this open site is just
Equation B-36
H f ( O(s) ) = H f ( Ga(s) ) H f ( Ga(b) )
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Figure B-4
Illustration of an Adsorption Reaction using the Atomic Site Formalism
Figure B-5
Illustration of an Adsorption Reaction using the Open Site Formalism
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B.2.2
Surface Reaction Expressions and Equations

This section presents expressions and equations that are useful in formulating chemically reacting flow problems. Species can exist in the gas phase, on surface sites, or in bulk mixtures. In some cases it is desirable to refer to information about species without regard to the phases, and in other cases it is desirable to determine information about species in one particular phase or group of phases. Therefore, before beginning to discuss our formalism in terms of mathematical expressions, we introduce a nomenclature that facilitates manipulating species information. Information about a species (say a thermodynamic property) is presumed to be available in ordered arrays beginning with the first gas-phase species, continuing through the surface species, and ending with the last bulk species. In the expressions and equations below we presume that there are K species, and we use the index k to refer to a specific species. There are K g gas-phase species, which, by convention, are always the first entries in the species arrays. The index of the first gas-phase f f species is K g ( K g = 1 by our convention) and the last gas-phase species index is l l f l K g ( K g = K g ). Thus, the gas-phase species indices are K g k K g . In a similar way f l surface species indices are in the range K s k K s and bulk species are in the range f l K b k K b . The surface species may be arranged on any number of sites, and the bulk species may exist in any number of bulk mixtures. Furthermore, situations can occur in which there are no surface species and/or no bulk species. As discussed in Section B.2.1, the species are grouped in phases. The first is the gas phase, whose index n = 1 . The next N s phases (if they are present) are the f l surface sites, whose phase indices are bounded by N s n N s . The final N b phases f l are the bulk mixtures, whose indices are bounded by N b n N b . In each phase n there are K phase ( n ) species, and those species have indices in the range f l K (n) k K (n) .
phase phase
B.2.3
Concentration Units
In a later section we discuss mass-action kinetics, where the rate-of-progress of reactions depends on molar concentrations either in the gas phase or on surface sites and activities in the bulk phases. However, for the purposes of formulating and solving the conservation equations that describe physical situations, it is often more natural to use gas-phase mass fractions and surface site fractions as dependent variables. Therefore, it is important to establish the rules for converting between the different ways to describe the composition of the gas and the surface. For the gas-phase species the molar concentrations [ X k ] (in mole/cm3) are written as
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Equation B-37
[ Xk ] = Yk Wk
( k = K g, , K g )
where the Y k are the mass fractions, is the gas-phase mass density, and the W k are the molecular weights. On the surface sites we can describe the composition in terms of an array of surface species site fractions Z k . This array is of length K s . It is composed of N s subunits of the site fractions of each of the species on a given site (phase) n . The site fractions on each site are normalized
Equation B-38 K s( n)
l
k = K s( n)
f
Zk ( n ) = 1
( n = N s, , N s )
The sum in Equation B-38 runs from the first species in phase n to the last species in phase n . The surface molar concentration of a species is then
Equation B-39
[ Xk ] = Zk ( n ) n k ( n )
where n is the density of sites of phase n (in mole/cm2) and k ( n ) is the number of sites that each species k occupies. For the sake of parallelism, we adopt the nomenclature for bulk species
Equation B-40
[ Xk ] = ak
( k = K b, , K b )
It is at best an approximation that bulk species form an ideal solution. Therefore, the concept of an activity (and the standard state to which it refers) must be introduced at the outset. In the limiting case of an ideal solution, the activity of a species is equal to its mole fraction. CHEMKIN-CFD assumes that the activity, a k , of bulk species k is used in all chemical rate expressions.
B.2.4
Surface Reaction Rate Expressions

The I reversible (or irreversible) surface reactions that involve K chemical species and can be represented in the general form
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Equation B-41 K K
'ki k ''ki k
k=1 k=1
( i = 1, , I )
The stoichiometric coefficients for elementary reactions ki are integers and k is the chemical symbol for the k th species. Usually, an elementary reaction involves only three or four species; hence the ki matrix is quite sparse for a large set of reactions.
Global reactions are sometimes stated with non-integer stoichiometric coefficients. CHEMKINCFD can accommodate non-integer stoichiometric coefficients.
(in mole/cm2/sec) for each of the K species (regardless of The net production rate s k phase) is the sum of the rate-of-production for all reactions involving the k th species
Equation B-42 I
= s k
where
Equation B-43
ki qi
i=1
( k = 1, , K )
ki = '' ki ' ki
The rate-of-progress variable q i for the i th reaction is given by the difference of the forward rates and the reverse rates
Equation B-44 K
q i = k fi [ X k ]
k=1
' ki
k ri [ X k ]
k=1
'' ki
The production rate n (in mole/cm2/sec) for each surface phase is

Equation B-45
n =
where
( n, i ) qi
i=1
( n = N s, , N s )
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Equation B-46 Ks ( n )
l
( n, i ) =
k = Ks ( n )
f
ki k ( n )
The term ( n, i ) is the net change in number of surface sites of type n for surface reaction i . As discussed above, the form of the concentrations [ X k ] depends upon whether species k is in the gas phase, on the surface, or in the bulk. Furthermore, the units of the rate constants will depend on the reactants and products in a particular reaction. As for gas-phase reactions, the forward rate constants k fi for the I reactions are (by default) assumed to have the following Arrhenius temperature dependence
Equation B-47
Ei -------k fi = A i T i exp R c T
where the pre-exponential factor A i , the temperature exponent i , and the activation energy E i are specified. These three parameters are required input to the SURFACE KINETICS Pre-processor for each reaction. There are a number of ways in which the rate expression for a reaction can be altered, which are summarized below.
Two gas constants, R and R c are used throughout this manual. R c is used only in conjunction with the activation energy E i and has compatible units. The reason for the duality is that many users would rather use different units (e.g. cal/mole) for the activation energies even though other units (e.g. ergs/mole) are used elsewhere.
For reversible reactions, the reverse rate constants k ri are related to the forward rate constants through the equilibrium constants as
Equation B-48
k fi k ri = -----K ci
The user can over-ride the use of Equation B-48 by explicitly declaring Arrhenius coefficients for the reverse reaction in the SURFACE KINETICS input via the auxiliary keyword REV.
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Although K ci is given in concentration units, the equilibrium constants are more easily determined from the thermodynamic properties in pressure units, K pi . They are related by
Equation B-49
K ci P atm = -------- RT
k=1
Kg
l K s(n) ki
l s
o ( n)
f
f k = K s(n)
ki
K s( n)
l
n=Ns
k = K s( n)
f
k ki K pi
o
where P atm denotes a pressure of 1 atm, and n is the standard-state surface site density of site type n . The sum in the first exponent runs only over the gas-phase species, and the sum in the second exponent runs only over surface species in surface phase n . The equilibrium constant K pi is obtained from the standard-state Gibbs free energy of reaction,
Equation B-50
K pi B.2.4.1
S i H i - --------- = exp -------RT R
Non-integer Stoichiometric Coefficients

For many real-world applications the elementary reactions are not known. Instead, the kinetics may only be summarized in terms of global expressions. GAS-PHASE KINETICS and SURFACE KINETICS input may therefore include use of non-integer stoichiometric coefficients.
Figure B-6
Examples of reactions with such non-integer coefficients
H(s) 0.5H2(g) C2H6 0.72C2H4 + 0.56H + 0.28CH4 + 0.28CH2 The rate-of-progress of a reaction is, by default, still evaluated via Equation B-44, with the coefficients ' ki and '' ki defined as real numbers instead of integers. The GASPHASE KINETICS and SURFACE KINETICS Pre-processors automatically allow real coefficients for reactions without requiring any special flags or keywords.
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B.2.4.2
Arbitrary Reaction Order

By default the rate-of-progress of a reaction is evaluated by Equation B-44, which uses the concentration of each reactant or product species raised to the power of its stoichiometric coefficient. Thus, the rate-of-progress of a reaction that includes species A with a coefficient of 2 will be second-order with respect to the concentration of A. Equation B-44 would always be valid when mass-action kinetics are obeyed, and the mechanism is written in terms of elementary reactions. However, often in real-world applications the elementary kinetics are not known. In some cases, an experimental measurement finds that the rate of reaction is proportional to the concentration of a species raised to some arbitrary power (different from its stoichiometric coefficient). Using the arbitrary-reaction-order option, the user may declare that the rate-of-progress of a reaction is proportional to the concentration of any species (regardless of whether that species even appears as a reactant or a product in the reaction) raised to any specified power. To modify the reaction order for the reaction in the forward or reverse direction, the user must declare the FORD or RORD auxiliary keywords, respectively, in the input file, as described in Section A.2.4.3.7. When the reaction-order-dependence of reaction i is changed via the FORD or RORD auxiliary keywords, the rate-of-progress variable q i for the reaction is evaluated by:
Equation B-51 K K F ki
q i = k fi [ X k ]
k=1
k ri [ X k ]
k=1
R ki
where F ki is the reaction order specified through the FORD keyword and R ki is the reaction order specified through the RORD keyword for species k . The default for species participating in reaction i is the normal mass-action kinetics values:
Equation B-52
F ki = ' ki
Equation B-53
R ki = '' ki
if an order-change parameter is not given for species k participating in that reaction.
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The user is advised to exercise caution when specifying a change of reaction order. Such a change may produce unexpected and unphysical results in a kinetic simulation. The user should also consider the kinetics of the reverse reaction when changing reaction-orders for the forward reaction. For example, such a reaction may no longer satisfy microscopic reversibility. At equilibrium, elementary kinetics ensure that
Equation B-54 K
k ri k=1 ----- = --------------------------- = K k fi '' ki [ Xk ]

k=1
[ Xk ]
' ki
K
[ Xk ]
k=1
' ki '' ki
A reaction for which one has specified an arbitrary reaction order will not have the proper equilibrium behavior unless
Equation B-55
F ki R ki = ' ki '' ki
( k = 1, , K )
The user specifying F ki may also wish to adjust R ki such that Equation B-55 is satisfied; the software does not do this automatically. Another alternative would be to simply specify that the reaction is irreversible, in which case the details of the reverse reaction become irrelevant.
B.2.4.3
Surface-Coverage Modification of Rate Expression

In some cases there are experimental data that indicate that the Arrhenius expression for the rate constant, Equation B-47, is modified by the coverage (concentration) of some surface or bulk species. The user may specify optional coverage parameters for species k and reaction i , through use of the auxiliary keyword COV. In this case, the rate constant for the forward reaction is modified as
Equation B-56
E i k fi = A i T i exp ------ RT
K s( N s)
l l
k = K s(N s)
f f
10
ki [ Z k ( n ) ]
ki [ Z k ( n ) ] - [ Z k ( n ) ] ki exp --------------------------RT
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where the three coverage parameters are ki , ki , and ki for species k and reaction i . The product in Equation B-56 runs over only those surface species that are specified as contributing to the coverage modification. Note that the surface site fractions appear in Equation B-56 rather than molar concentrations [ X k ] (mole/cm2) for surface species, while bulk activities appear for bulk species. The term associated with ki now makes it possible for the rate-of-progress of a reaction to be proportional to any arbitrary power of a surface species concentration. Also, using this modified expression for k fi , the net pre-exponential factor may be a function of coverage
Equation B-57 K s( N s)
l l
log 10 A = log 10 A i +
k = K s(N s)
f f
ki [ Z k ( n ) ]
and the activation energy is a function of the coverage

Equation B-58 Ks ( Ns )
l l
E = Ei +
k = Ks ( Ns )
f f
ki [ Z k ( n ) ]
For reactions with optional coverage dependence, the rate of progress is calculated employing Equation B-44, with the forward rate coefficient from Equation B-56. If the form of Equation B-56 is not flexible enough to describe a certain coverage behavior, one can repeat the same reaction several times with different values for the coverage parameters such that the sum of the rate constants approximates the desired form.
B.2.4.4
Sticking Coefficients
For some simple surface reaction mechanisms we have found it convenient to specify the surface reaction rate constant in terms of a sticking coefficient (probability).
Because i is defined as a probability, it must lie between 0 and 1 to make physical sense. Therefore, CHEMKIN-CFD checks the value of i , and an unphysical sticking coefficient greater than 1 is changed to the value 1.
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For example, one might have a measurement or intuition about the probability that a certain process takes place when a given collision occurs. For consistency in expressing each surface reaction in terms of a rate constant, we provide a conversion between this sticking coefficient form and the usual rate expression. We allow the sticking coefficient form only for the simple case of a surface reaction in which there is exactly one gas-phase reactant species, although there can be any number of surface species specified as reactants. The sticking coefficients functional form is taken to be
Equation B-59
i = min [ 1, a i T i e
b ci Rc T
In this case, a i and b i are unitless and c i has units compatible with R c . CHEMKINCFD also allows for surface-coverage modification of a sticking coefficient, analogous to Equation B-56. We give three successively complex examples of using sticking coefficients. First, to specify that SiH2(g) reacts with probability i upon each collision with the surface, one could write the reaction as in Figure B-7.
Figure B-7 Example of Sticking-coefficient Reaction with No Surface Species
SiH2(g) Si(b) + H2 In this example, we have not explicitly included the surface in writing the reaction. A somewhat more detailed way of using the sticking-coefficient specification would be to say that SiH2(g) reacts with probability i upon each collision with a bare surface silicon atom, Si(s), as in Figure B-8.
Figure B-8 Example of Sticking-coefficient Reaction with a Surface Site
SiH2(g) + Si(s) Si(s) + Si(b) + H2 If the surface site fraction of Si(s) were unity, then a fraction i of the collisions of SiH2 with the surface would result in a reaction. However, for Si(s) coverages less than 1, the reaction rate decreases in proportion with the coverage of Si(s). In a third (contrived) example, suppose there is a probability i for a reaction to occur when SiH2 collides with both a Si(s) and a C(s) site, as in Figure B-9.
Figure B-9 Example of Sticking-coefficient Reaction with Multiple Surface Sites
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SiH2(g) + Si(s) C(s) Si(b) + SiH(s) + CH(s) The rate of this reaction would be proportional to both the coverage of Si(s) and C(s). To convert rate constants given as sticking coefficients i to the usual mass-action kinetic rate constants there is the relation
Equation B-60
RT =1 ------------------ ------------k fi = i j m 2W k ( tot )

where R is the universal gas constant, W k is the molecular weight of the gas-phase species, tot is the total surface site concentration summed over all surface phases (number of moles of surface sites per unit area), and m is the sum of all the stoichiometric coefficients of reactants that are surface species. The term involving tot raised to the m power is needed to convert from the unitless sticking coefficient form to units appropriate for a rate constant, and the term in the square root accounts for the gas/surface collision frequency. In the third example given above, Equation B-9, the value of m is 2, because there are two surface sites appearing as reactants, i.e., Si(s) and C(s). The product term in Equation B-60 is the product of the site-species occupancies, raised to a power equal to the reaction order for that species, for all site species that are reactants. Here, j is the number of sites that the surface species occupies, and j is the reaction order for that species. The product term will be equal to one when there are unity site occupancies for all of the surface species in the reaction. Implicit in the sticking coefficient description just presented is an assumption that the sticking coefficient is relatively small, i.e., much less than one. In this case the molecular motion in the vicinity of the solid surface is random and the collision frequency of gas-phase species with the surface is not affected by the surface itself. However, when the sticking coefficient is large, i.e., close to one, then the velocity distribution becomes skewed. Species whose random motion carries them close to the surface have a high probability of staying there, which causes a non-Maxwellian velocity distribution that, in turn, alters the net species flux near the surface. Motz and Wise9 (p. 63) analyzed this situation and provided a correction factor that modified Equation B-60 as
' ji
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Equation B-61
i RT =1 ------------------ ------------k fi = ------------------- j m 2W 1 i 2 k ( )

tot
' ji
The rate-of-progress is calculated using Equation B-44, as usual. The sticking coefficient specification is only allowed for the forward reaction. If the reaction is written as reversible, the reverse reaction rate constant would be calculated from Equation B-61 and Equation B-48 using microscopic reversibility.
B.2.4.5
Langmuir-Hinshelwood and Eley-Rideal Reactions

Surface reactions are often described using global reactions rather than as a series of elementary reactions. Some of the most common global rate expressions used for surface reactions are the Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) rate expressions. The former applies to the case where adsorption and desorption are assumed to be in equilibrium, and a reaction on the surface between adsorbed species is rate determining. The latter applies to the case of a reaction between a gas-phase species and an adsorbed species being rate-limiting. Although originally developed for specific cases, these names are now used to refer to a variety of rate expressions with similar forms. If a LH reaction is used, a single global reaction might constitute the entire surface chemistry mechanism. The "Langmuir" part of the name for the LH rate expression originates from the inclusion of the Langmuir adsorption isotherm, which assumes that the adsorption sites on the surface are independent from each other (single site adsorption), the sites are equivalent, and the surface coverage decreases the number of sites available for adsorption only, but does not alter the energetics of adsorption/desorption. The following example of a LH reaction illustrates its features. Species A and B coadsorb onto the surface, react to products C and D, which can then desorb. The reaction between adsorbed A and adsorbed B is assumed to be rate-limiting and irreversible, while the adsorption/desorption processes are assumed to be in equilibrium. In the LH formulation, the elementary chemical reactions shown in Figure B-10 would be replaced by the single overall reaction shown in Figure B-11, which does not explicitly include any surface species.
Figure B-10
Langmuir-Hinshelwood Elementary Chemical Reactions
A + O(s) A(s) B + O(s) B(s) A(s) + B(s) C(s) + D(s) C(s) C + O(s) D(s) D + O(s)
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Figure B-11
Langmuir-Hinshelwood Single Overall Reaction
A+BC+D The effects of surface-sites being blocked by various species are included via the adsorption/desorption equilibria. This "lumping" of a number of elementary steps together results in a rate expression that differs substantially from a simple massaction rate expression. The rate of progress variable is given by:
Equation B-62
kK A [ X A ] K B [ X B ] q = --------------------------------------------------------------------------------------------------------------2 ( 1 + KA [ XA ] + KB [ XB ] + KC [ XC ] + KD [ XD ] )
where the K s are the equilibrium constants for the adsorption/desorption steps and [ X i ] s are the concentrations of the species. As product species, C and D do not appear in the numerator, but as adsorbed species they can block surface sites, so they do appear in the denominator. The k is expressed in terms of Arrhenius parameters, as are the K s. The equilibrium constant is defined as K = AT exp ( H RT ) , in parallel with the standard expression for rate constants. Often, the equilibrium constants in the numerator are lumped into the rate constant, giving:
Equation B-63
k [ XA ] [ XB ] q = --------------------------------------------------------------------------------------------------------------2 ( 1 + KA [ XA ] + KB [ XB ] + KC [ XC ] + KD [ XD ] )
The generalized form of the above expression is:
Equation B-64
[ Xi ]
i q = k -------------------------------------- 2 1 + K i [ X ] i i
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where i represents gas-phase species in the reaction, and the exponent of 2 in the denominator comes from the fact that the reaction rate is determined by the reaction between two adsorbed species. In practice, this rate form is often used for empirical parameter fitting, so we further generalize it to:
Equation B-65
[ Xi ]
li
i q = k ------------------------------------------m n i 1 + Ki [ Xi ] i
where: 1. the chemical species in the rate law are not limited to the reactants and products in the reaction description, 2. the exponents ( l i ) for the chemical species concentrations in the numerator of Equation B-65 may differ from the stoichiometric coefficients ( i ) and may be fractional, 3. the overall exponent in the denominator ( m ) of Equation B-65 may differ from 2, and may be fractional, 4. the exponents ( n i ) for the concentrations of species in the denominator may differ from 1 or the stoichiometric coefficients, and may be fractional. Eley-Rideal (also called Rideal-Eley) reactions are less common than LH reactions. The following example illustrates its features. Species A adsorbs onto the surface, then reacts with gas-phase species B to produce C, which can then desorb. The reaction between adsorbed A and gas-phase B is assumed to be rate-limiting and irreversible, while the adsorption/desorption processes are assumed to be in equilibrium. In the ER formulation, the elementary chemical reactions shown in Figure B-12 would be replaced by the single overall reaction shown in Figure B-13, which does not explicitly include any surface species.
Figure B-12 Eley-Rideal Elementary Chemical Reaction
A + O(s) A(s) A(s) + B(g) C(s) C(s) C + O(s)

Figure B-13 Eley-Rideal Single Overall Reaction
A+BC
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In this case, the rate of progress variable is given by:

Equation B-66
kK A [ X A ] [ X B ] q = ---------------------------------------------------------( 1 + KA [ XA ] + KC [ XC ] )
or
Equation B-67
k [ XA ] [ XB ] q = ---------------------------------------------------------( 1 + KA [ XA ] + KC [ XC ] )
The generalized form of this is:
Equation B-68
[ Xi ]
i q = k ----------------------------------- 1 + K i [ X ] i i
which is the same as the Equation B-64 above for LH kinetics, except that the denominator has an overall exponent ( m ) of one rather than two. ER reactions are thus treated as a special case of the LH rate law. Using the LH option requires paying careful attention to the units of the reaction rates. The discussion above assumes that the rate expressions are given in terms of gas concentrations, which is the standard for GAS-PHASE KINETICS. However, literature values for LH rate parameters, especially equilibrium constants, are often provided in pressure units. To reduce the number of units conversions required of the user, equilibrium constants may be input in either pressure units or concentration units. This option is currently limited to the LH rate expression and only for the equilibrium constants. Rate parameters still must be input in concentration units. In SURFACE KINETICS INPUT, the default units, unless altered on the REACTION line, for the rate of a reaction are moles cm-2sec-1. Rate parameters given in pressure units, for example in atm sec-1, do not have the same dimensions as moles cm-2sec-1. Such a rate would need to be divided both by RT and the surface-area to volume ratio ( AV ), before use. Rates given in terms of weight of catalyst need to be converted to a rate expressed in terms of the effective surface area of the catalyst via the surface area per unit weight of catalyst and the dispersion. Rates given on a per site basis should also be converted to a per area basis.
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C
C.1
Nomenclature
Latin Equation Symbols
The table below shows the conventions used in this document for latin symbols.
Table C-1 Latin Symbols
Symbol ai ak a nk a Ai
Description
Pre-exponential factor in sticking coefficient expression Activity of the k th bulk-phase species Coefficients of fits to thermodynamic data Mean specific Helmholtz free energy of a mixture Pre-exponential factor in the rate constant of the i th reaction
CGS Units
none none depends on ergs/g depends on reaction
bi ci
Temperature exponent in sticking-coefficient expression Activation energy in sticking-coefficient expression. By default, GAS-PHASE KINETICS INPUT and SURFACE KINETICS input uses activation energies in calories instead of ergs.
none cal/mole
c pk
Specific heat capacity at constant pressure of the k th species
ergs/(g K)
c pk, int.
Internal contribution to the mass specific heat of the k th species
ergs/(g K)
c pk, rot.
Rotational contribution to the mass specific heat of the k th species
ergs/(g K)
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May 2009
Chapter C: Nomenclature
Table C-1 Latin Symbols (Continued)
Symbol c vk
Description
Specific heat capacity at constant volume of the k th species
CGS Units
ergs/(g K)
cp cv C pk
o
Mean specific heat capacity at constant pressure Mean specific heat capacity at constant volume Molar heat capacity at constant pressure of the k th species
ergs/(g K) ergs/(g K) ergs/(mole K)
C pk
Standard state molar heat capacity at constant pressure of the species
ergs/(mole K)
C pk, trans.
Translational contribution to the molar heat capacity of the k th species
ergs/(mole K)
C pk, vib.
Vibrational contribution to the molar heat capacity of the k th species
ergs/(mole K)
C pk, rot.
Rotational contribution to the molar heat capacity of the k th species
ergs/(mole K)
C vk Cp Cv C k Dk
T
Molar heat capacity at constant volume of the k th species Mean molar heat capacity at constant pressure Mean molar heat capacity at constant volume Chemical creation rate of the k th species Thermal diffusion coefficient of the k th species Ordinary multicomponent diffusion coefficient of the species k in species j
ergs/(mole K) ergs/(mole K) ergs/(mole K) mole/(cm3 sec) g/(cm sec) cm2/sec
D k, j D kj D km D k
Binary diffusion coefficient of species k in species j Mixture-averaged diffusion coefficient of the k th species Chemical destruction rate of the k th species
cm2/sec cm2/sec mole/(cm3 sec)
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Nomenclature
Symbol Ei
Description
Activation energy in the rate constant of the i th reaction. By default, GAS-PHASE KINETICS input and SURFACE KINETICS input uses activation energies in calories instead of ergs.
CGS Units
cal/mole
F ki
Forward reaction-order specified for the k th species in i th reaction
none
hk h Hf Hk Hk H I kB k fi k ri K Kb K b(n) K b(n) K ci
l f o
Specific enthalpy of the k th species Mean specific enthalpy of a mixture Enthalpy of formation Standard state molar enthalpy of the k th species Molar enthalpy of the k th species Mean molar enthalpy of a mixture Total number of reactions Boltzmann Constant Forward rate constant of the i th reaction Reverse rate constant of the i th reaction Total number of species Total number of bulk species Index of the first bulk-phase species in phase n Index of the last bulk-phase species in phase n Equilibrium constant in concentration units for the i th reaction
ergs/g ergs/g ergs/mole ergs/mole ergs/mole ergs/mole none ergs/K depends on reaction depends on reaction none none none none depends on reaction
Kg Kg Kg
l f
Total number of gas-phase species Index of the first gas-phase species Index of the last gas-phase species
none none none
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Symbol K pi Ks K s(n) K s(n) K phase m jk mk [M] N

l f
Description
Equilibrium constant in pressure units for the i th reaction Total number of surface species Index of the first surface species in phase n Index of the last surface species in phase n Array containing the number of species in each phase Reduced molecular mass for the collision Molecular mass of the k th species Total molar concentration of a mixture Number of coefficients in polynomial fits to C p R Total number of phases
o
CGS Units
depends on reaction none none none none g g mole/cm3 none none none none none none none none none none dynes/cm2 dynes/cm2 mole/(cm2 sec) ergs/(mole K)
NA Nb Nb Nb Ng Ns Ns Ns P P atm qi R
l f l f
Avogadros number Total number of bulk phases Index of the first bulk phase Index of the last bulk phase Number of gas phases (always equal to 1) Total number of surface site types (phases) Index of first surface phase Index of last surface phase Pressure Pressure of one standard atmosphere Rate of progress of the i th reaction. Universal gas constant
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Nomenclature
Symbol Rc
Description
Universal gas constant, in units consistent with activation energy
CGS Units
[cal/(mole K)]*
R ki
o
Reverse reaction-order specified for the k th species in the i th reaction.
none
sk s s k
Standard state specific entropy of the k th species Mean specific entropy of a mixture Production rate of the k th species from surface reactions Standard state molar entropy of the k th species Molar entropy of the k th species Mean molar entropy of a mixture Temperature
ergs/(g K) ergs/(g K) mole/(cm2 sec) ergs/(mole K) ergs/(mole K) ergs/(mole K) K none none K cm/sec cm/sec g/mole g/mole cm/sec none none mole/cm3
Sk Sk S T
T ik Tk
*
Reduced temperature for the collision Reduced temperature of the k th species Ambient temperature Diffusion velocity of the k th species Ordinary diffusion velocity of the k th species Mean molecular weight of a mixture Molecular weight of the k th species Thermal diffusion velocity of the k th species Array of surface species mole fractions Mole fraction of the k th species Molar concentration of the k th species
To Vk Vk W Wk Wk X Xk [ Xk ]
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115
Symbol Yk Z Zk ( n )
Description
Mass fraction of the k th species Array of surface species site fractions Site fraction of the k th species on surface phase n
CGS Units
none none none
The energy CGS units that are noted by an asterisk (*) depend upon user input at the
REACTION line or in the UNITS auxiliary keyword for chemistry input files. The default unit is
calories.
C.2
Greek Equation Symbols

The table below shows the conventions used in this document for Greek symbols.
Table C-2 Greek Symbols
Symbol
Description
Parameter in mechanism Polarizability of the k th species Reduced polarizability of the k th species. Enhanced third-body efficiency of the k th species in the i th reaction
CGS Units
none 3 none none
i k k
*
ki i n n tot n i
Temperature exponent in the rate constant of the i th reaction Site density for surface phase n Initial site density for surface phase n Site density summed over all surface phases Production rate for surface phase n Sticking coefficient for the i th surface reaction
none
mole/cm2 mole/cm2 mole/cm2 mole/(cm2 sec) none
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Nomenclature
Table C-2 Greek Symbols (Continued)
Symbol
Description
Reduced dipole moment of the k th species Effective reduced dipole moment for the collision Small number (e.g. 1.E-12) Emissivity
CGS Units
none none none none ergs
jk k
*
jk k ki k ki 0 k jk k k
*
Effective Lennard-Jones potential well depth for the collision Lennard-Jones potential well depth for the k th species Coverage parameter Mixture viscosity Pure species viscosity of the k th species Coverage parameter Bulk coefficient of viscosity Thermal conductivity of the gas mixture Multicomponent thermal conductivity of the species Thermal conductivity of the k th species Effective dipole moment for the collision Dipole moment of the k th species Reduced dipole moment of the k th species Coverage parameter Relaxation collision number Mass density of a gas mixture Mass density of the k th bulk species
ergs [cal/mole K]* g/(cm sec) g/(cm sec) none g/(cm sec) ergs/(cm sec K) ergs/(cm sec K) ergs/(cm sec K) Debye Debye none none none g/cm3 g/cm3
ki ij k
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117
Table C-2 Greek Symbols (Continued)
Symbol
Description
Number of sites occupied by the k th species. Lennard-Jones diameter of the k th species
CGS Units
none none
jk ki ki ki k
k
Effective Lennard-Jones diameter for the collision Net stoichiometric coefficient of the k th species in the i th reaction; ki = ki ki Stoichiometric coefficient of the k th reactant species in the i th reaction Stoichiometric coefficient of the k th product species in the i th reaction Chemical symbol of the k th species Collision integral Chemical production rate of the k th species due to gasphase reactions
none
none
none none mole/(cm3 sec)
The energy CGS units that are noted by an asterisk (*) depend upon user input at the
REACTION line or in the UNITS auxiliary keyword for chemistry input files. The default unit is
calories.
C.3
Subscript Equation Symbols

The table below shows the conventions used in this document for subscript symbols.
Table C-3 Subscript Symbols
Symbol
Description
Denotes reaction index, ionic species index, or inlet index. Species index
i k
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Nomenclature
Table C-3 Subscript Symbols (Continued)

Symbol
Description
Phases index Species index for a non-polar species
Species index for a non-polar species
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Index
Index
A
activation energy 99, 103 activity 97 bulk species 92, 97 gas species 93 site species 93 adsorption 91, 93, 95, 106 arbitrary reaction order 68, 81, 101 argon methane combustion mechanism 34 Arrhenius rate parameters 62, 63, 64, 65, 66, 67, 68, 71, 72, 74,
99, 107
error checks 74 examples of 72 keywords
atomic site formalism 94, 95 auxiliary data 67, 68, 70 gas-phase reactions error checks 57 examples of 54 keywords
COV 68, 71, 102 DUP 68, 71, 74 FORD 68, 71, 74, 101 LANG 72 LHDE 72 LHNU 72 LHPR 72 MWOFF 66, 68, 72 MWON 66, 68, 72 NONCON 74 REV 67, 71, 99 RORD 68, 71, 74, 101 STICK 65, 67, 68, 71 UNITS 69, 71, 74
summary of the rules 71
CHEB 51 DUP 52 FORD 52 HIGH 50 LT 51 MWOFF 64 MWON 64 PCHEB 51 PLOG 51 REV 52 RLT 51 RORD 52 TCHEB 51 UNITS 52
Lindemann formulation of pressure dependence 50 summary of the rules for gas-phase reactions 55 surface reactions 64
B
balance elemental 94 site 94 blank lines 59 spaces 64, 66, 71 bulk data 60, 63 error checks 73 examples 62 summary of the rules for 61 density 73 mixture 92, 93 names 61 phase 58, 60, 92, 96
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May 2009
Index
species 58, 60, 92, 93, 96, 97 activity 92, 97
C
capacity, heat 62 CHEB 51, 57 Chebyshev polynomial rate expressions 51, 88, 89 Gauss-Chebyshev grid 89 chemical potential 92, 93 reactions 63, 93 symbol 98 chemically activated bimolecular reactions 86 chemistry mechanisms 33 gas-phase reaction 46 surface reaction 63 chemistry set. See chemistry mechanisms. CHEMKIN 9, 16 CKUPROD 46 CKUPROG 53 coefficients 65 non-integer stoichiometric 98, 100 sticking 64, 65, 67, 68, 72, 74, 103, 105 stoichiometric 66, 68, 71, 73, 74, 98, 101, 105 collision 104 diameter Lennard-Jones 76 frequency 105 number, rotational relaxation 77 comments 60, 61, 64, 67, 72 computational fluid dynamics 9 concentration molar 96 surface molar 97 surface site 105 units 96, 100 condensed-phase species 60 configuration, geometrical 76 conservation charge 91 elemental composition 91 equations 96 mass 91 of mass and surface sites 91 constants equilibrium 99, 100 forward rate 99 reverse rate 99 surface reaction rate 103 universal gas 105 continuation next line 66 correction
factor 105 Motz-Wise 64, 66, 68, 72 COV 68, 71, 72, 75, 102 coverage parameters 68, 71, 102, 103
D
data auxiliary 64, 67, 68, 70 bulk 60, 63 chemistry mechanisms element 41 reaction 64 site 58, 63 thermodynamic 62, 63 transport for gas-phase species 77 default units 65, 69, 71 delimiters 65, 74 density bulk 73 mass 61 sites of phase 97 slash-delimited 58 standard-state site 58, 60 surface site 100 deposition 91 desorption 91, 93, 106 diagnostic messages 73 dilution 92 dipole moment 76 Directed Relational Graph method 34 distribution, velocity non-Maxwellian 105 dummy thermodynamic data 62 DUP 52, 56, 68, 71, 74 duplicate reactions 52, 67
E
efficiency, third body 49 element data 41 error checks 56 summary of the rules for 43 elemental balance 94 composition 91 elementary reactions 91, 100, 101 elements 59, 74, 94 ELEMENTS section of gas-phase chemistry file 42 Eley-Rideal reactions 69, 72, 106 energy activation 99, 103 Gibbs free 100
122
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Index
Chemkin-CFD for FLUENT Manual
of reaction 100 units 63, 69, 71 enthalpy 62 entropy 62 equations chemical potential 92 conservation 96 Greek symbols 116 Latin symbols 111 subscript symbols 118 equilibrium behavior 102 constants 99, 100, 107 error checks 73 auxiliary data, gas-phase reactions 57 auxiliary data, surface reactions 74 bulk data 73 element data 56 reaction data 56, 74 site data 73 species data 56 thermodynamic property data 56, 73 etching 91 ethane chemistry mechanism 33 examples auxiliary data, gas-phase reactions 54 auxiliary data, surface reactions 72 bulk data 62 reaction data 48, 66 site data 59 exponent, temperature 72, 99 expressions, rate global 100 reverse 67
free energy Gibbs 100 frequency, collision 105
G
gas-phase 96 mass density 97 reaction data species 58, 60, 61, 63, 67, 74, 93, 96, 100, 105 activity 93 indices 96 gas-phase kinetics input 41, 45, 46, 55, 63, 76, 81 pre-processor 59, 63, 74, 100 Gauss-Chebyshev grid 89 geometrical configuration 76 Gibbs free energy 100 global rate expressions 98, 100 Greek equation symbols 116 grimech30_50spec 34
H
H2_mech 34 heat capacity 62 of formation 94 Henrys law 92 HIGH 50, 57 hydrogen chemistry mechanism 33 hydrogen combustion mechanisms 34
I
ideal solution 97 index bulk species 96 first gas-phase species 96 last gas-phase species 96 surface species 96 input gas-phase kinetics 41, 45, 46, 55, 63, 76, 81 surface kinetics 57, 58, 62, 64, 75, 99 thermodynamic property data 39 transport property data 76 installation manual 11 Installation and Licensing Manual 11 installing 13 irreversible reactions 65, 74
F
factor correction 105 pre-exponential 72, 99, 103 sticking coefficient 74 Fluent 9 FORD 52, 54, 68, 69, 71, 72, 74, 81, 82, 101 formalism atomic site 94, 95 mathematical 91 open site 94, 95 format free 64 forward rate constants 99 fractions mass 96 mole 92, 93, 97 site 92, 93, 96, 97, 103, 104
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123
Index
K
keywords auxiliary gas-phase reactions
UNITS
52
auxiliary data gas-phase reactions 55
CHEB 51 DUP 52 FORD 52 HIGH 50 LOW 50 LT 51 MWOFF 64 MWON 64 PCHEB 51 PLOG 51 REV 52 RLT 51 RORD 52 SRI 50 TCHEB 51 TROE 50
surface reactions
LANG 69, 70, 72, 75 Langmuir-Hinshelwood reactions 69, 72, 106 Latin equation symbols 111 Lennard-Jones collision diameter 76 potential well depth 76 LHDE 70, 72 LHNU 70, 72 LHPR 70, 72 Li et al. 34 licensing 13 manual 11 Lindemann formulation of pressure-dependent reaction 50 lines, blank 59 LOW 50, 57 LT 51, 57
M
manual installation and licensing 11 mass density 61 density, gas-phase 97 fractions 96 mass-action kinetics 91, 96, 101 rate constants 105 material declaration 58 mathematical formalism 91 mechanisms See chemistry mechanisms. messages, diagnostic 73 methane chemistry mechanism 33 microscopic reversibility 102, 106 midpoint temperature 62 mixture bulk 92, 93 modification of rate expression, surface-coverage 102, 104 molar concentrations gas species 96 surface site species 97 mole fractions 93, 97 mole fractions 92 molecular weight 97, 105 Motz-Wise correction 64, 66, 68, 72 MWOFF 64, 66, 68, 72, 75 MWON 63, 66, 68, 72
COV 68, 71, 102 DUP 68, 71, 74 FORD 68, 71, 74, 101 LANG 72 LHDE 72 LHNU 72 LHPR 72 MWOFF 66, 68, 72 MWON 66, 68, 72 NONCON 74 REV 67, 71, 99 RORD 68, 71, 74, 101 STICK 65, 67, 68, 71 UNITS 69, 71, 74
kinetics data 33 kinetics, mass-action 91, 96, 101
L
Landau Teller 55 Landau-Teller reactions 51 Landau-Teller rate expressions 90 Landau-Teller reaction 51
N
names bulk 61 site 60
124
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Index
species 60, 61 net production rate 98 next line, continuation 66 nomenclature 111 NONCON 74 non-integer stoichiometric coefficients 98, 100 non-integer stoichiometric coefficients 98 non-Maxwellian velocity distribution 105
chemistry mechanisms 33 methane combustion mechanism 34 Propane-NOx_highT 34 properties thermodynamic 62, 91, 100 propyl radical methane combustion mechanism 34
Q
quick reference 79
O
occupancy number 59 site 59 open site 92, 94 formalism 94, 95 order reaction 52, 68, 71, 81, 101, 102, 105
R
Raoults law 92 rate constants 105 forward 99 mass-action kinetics 105 reverse 99 units 99 expressions Arrhenius 64, 65, 107 Chebyshev polynomial 51, 88, 89 Eley-Rideal 106 Landau-Teller 51 Langmuir-Hinshelwood 106 reverse 52 surface-coverage modification of 102 net production 98 production 98 rate of production, species 98 user-defined function 46, 64 rate of progress user-defined function 70 rate of progress, reaction 68, 96, 100 calculated 106 user-defined function 53, 70 variables 98, 101 rate of progress, reactions 103 reactants 65, 67, 94, 99 reaction adsorption 93, 95 chemical 63, 93 chemically activated bimolecular 86 data 64 criteria 65 error checks 56, 74 examples of 48, 66 summary of the rules 49, 66 duplicate 52, 67 elementary 9, 91, 100, 101 Eley-Rideal 106 global 98
P
parameters Arrhenius rate 62, 63, 64, 65, 66, 67, 68, 71, 72, 74, 107 coverage 68, 71, 102, 103 reaction order 52, 68 reverse rate 52, 71 PCHEB 51, 57 phase 92, 96 bulk 58, 60, 92, 96 density of sites 97 gas 96 indices 96 names 61 surface 58, 98, 100, 105 PLOG 51 polarizabilities 76 polynomial rate expressions Chebyshev 88, 89 potential, chemical 92, 93 pre-exponential factor 72, 99, 103 sticking coefficient 74 unit conversion 72 pre-processor, CHEMKIN-CFD 52, 56, 60 gas-phase kinetics 63, 74, 100 surface kinetics 57, 62, 68, 69, 72, 73, 75, 94, 99, 100 pressure 92 reactions that depend on 49, 83 units 100 probability 103 problems having no reactions 55 production rate, species 98 products 65, 67, 94, 99 propane
CFD-FLU-20091-0905-UG-1
125
Index
irreversible 65, 74 Landau-Teller 51 Langmuir-Hinshelwood 106 order 52, 68, 71, 81, 101, 102, 105 parameters pressure dependence 49 pressure-dependent 83 rate constants, surface 103 rate of progress 68, 96, 100, 103 user-defined function 53 reversible 65, 67, 71, 99 sticking-coefficient 63, 66, 68, 74 surface 58, 60, 61, 91, 94, 97, 99, 103 symbolic description 64 three-body 82 unimolecular/recombination fall-off 83 units 52 REACTION line 46, 47, 53 REACTIONS line 64, 70 real numbers as stoichiometric coefficients 100 results, unphysical 102 REV 51, 52, 54, 57, 67, 71, 72, 74, 99 reverse rate constants 99 parameters 52, 67, 71 reversibility, microscopic 102, 106 reversible reaction 52 reversible reactions 65, 67, 71, 99 RLT 51, 57 RORD 52, 68, 71, 72, 74, 81, 82, 101 rotational relaxation collision number 77 rules for auxiliary data, gas-phase reactions 55 for auxiliary data, surface reactions 71 for bulk data, summary 61 for element data, summary 43 for reaction data, summary 49, 66 for site data, summary 60 for species data, summary 44 for thermodynamic property data, summary 39
S
site balance 94 conservation 91 data 58, 63 error checks 73 examples 59 summary of the rules for 60 densities, surface 58, 100 fractions 92, 93, 96, 97, 103, 104 names 60 occupancy 59
of phase, density 97 open 92, 94 species activity 93 type 91, 92, 93 SKUPROD 64, 70 solution ideal 97 spaces, blank 64, 66, 71 species bulk 58, 60, 73, 92, 93, 96, 97 condensed-phase 60 data 77 error checks 56 summary of the rules 44 gas-phase 58, 60, 61, 63, 67, 74, 93, 96, 100, 105 indices 96 names 60, 61 site 73 surface 93 symbols 65 types bulk 91 gas-phase 91 surface 91 species rate of production user-defined function 46 SPECIES section of gas-phase chemistry file 44 SRI 50, 57 standard state bulk phase 92 site density 58, 60 STICK 65, 66, 67, 68, 71, 72, 75 sticking coefficients 63, 64, 65, 66, 67, 68, 72, 74, 103, 105 sticking-coefficient specification 104 stoichiometric coefficients 66, 68, 71, 73, 74, 98, 101, 105 non-integer 98, 100 subroutine user-defined reaction rate of progress 70 subscript equation symbols 118 summary of the rules auxiliary data, gas-phase reactions 55 auxiliary data, surface reactions 71 bulk data 61 element data 43 reaction data 49, 66 site data 60 species data 44 thermodynamic property data 39 surface layer 91 molar concentration 97 phase 58, 98, 100, 105
126
CFD-FLU-20091-0905-UG-1
Index
reaction mechanism 63 reaction rate constant 103 reactions 58, 60, 61, 91, 94, 97, 99, 103 site concentration 105 density 100 species 93 indices 96 surface kinetics input 57, 58, 62, 64, 75, 99 pre-processor 57, 67, 69, 72, 73, 94, 99, 100 surface reaction data surface-coverage modification of rate expression 102, 104 symbolic description of the reaction 64 symbols chemical 98 species 65
energy 63, 69, 71 pressure 100 rate constants 99 universal gas constant 105 unphysical results 102 user-defined function 70 CKUPROG 53 reaction rate of progress 53 SKUPROG 70 species rate of production 46 USRPROD keyword 46, 53, 64, 70 USRPROG keyword 53, 70 USRPROD 46, 64 USRPROG 53, 70
V
variables reaction rate of progress 98, 101 velocity distribution, non-Maxwellian 105
T
TCHEB 51, 57 temperature dependence, Arrhenius 99 exponent 72, 99 midpoint 63 THERMO data format 45 thermochemical data thermodynamic data 62, 63 dummy 62 properties 62 thermodynamic property data 39, 91, 100 error checks 56, 73 file 38 input 39 summary of the rules 39 third-body efficiency 49, 55 three-body reactions 82 transport data transport property data input 76 TROE 50, 57 tutorials 11 type of site 91, 92, 93
W
weight, molecular 97, 105
U
unimolecular/recombination fall-off reactions 83 UNITS 52, 65, 69, 71, 72, 74, 116, 118 units concentration 96, 100 conversion for pre-exponential factor 72 default 65, 69, 71
CFD-FLU-20091-0905-UG-1
127
Index
128
CFD-FLU-20091-0905-UG-1

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RELEASE 20091

CHEMKIN-CFD for FLUENT Manual

CHEMKIN-CFD for FLUENT Module

CHEMKIN-CFD for FLUENT

Getting Started with CHEMKIN-CFD ....................................................................................................................13

Chemical Reaction Mechanisms...........................................................................................................................33

Background Details for Working with Reaction Mechanisms .......................................................................37

CHEMKIN-CFD for FLUENT

Theoretical Background .........................................................................................................................................79

2009 Reaction Design

CHEMKIN-CFD for FLUENT

CHEMKIN-CFD for FLUENT

2009 Reaction Design

CHEMKIN-CFD for FLUENT

CHEMKIN-CFD for FLUENT

2009 Reaction Design

CHEMKIN-CFD for FLUENT

CHEMKIN-CFD for FLUENT

Contents of this Manual

2009 Reaction Design

CHEMKIN-CFD for FLUENT

Installation and Licensing Manual

2009 Reaction Design

CHEMKIN-CFD for FLUENT

2009 Reaction Design

CHEMKIN-CFD for FLUENT

Getting Started with CHEMKIN-CFD

CHEMKIN-CFD for FLUENT

Chapter 2: Getting Started with CHEMKIN-CFD

Enabling the CHEMKIN-CFD Module in FLUENT

We recommend running the CHEMKIN-CFD module in Double Precision.

FLUENT Graphical User Interface

2009 Reaction Design

Getting Started with CHEMKIN-CFD

CHEMKIN-CFD for FLUENT

2009 Reaction Design

CHEMKIN-CFD for FLUENT

Chapter 2: Getting Started with CHEMKIN-CFD

2009 Reaction Design

Getting Started with CHEMKIN-CFD

CHEMKIN-CFD for FLUENT

Setting Initial Conditions for Combustion Problems

Turbulence-Chemistry Interactions Models and CHEMKINCFD

2009 Reaction Design

CHEMKIN-CFD for FLUENT

Chapter 2: Getting Started with CHEMKIN-CFD

Controlling Parameters in the FLUENT Text User Interface

2009 Reaction Design

Getting Started with CHEMKIN-CFD

CHEMKIN-CFD for FLUENT

Text User Interface Commands for Changing CHEMKIN-CFD Parameters

2009 Reaction Design

CHEMKIN-CFD for FLUENT

Chapter 2: Getting Started with CHEMKIN-CFD

Absolute Tolerance for Gas-phase Species

Relative Tolerance for Gas-phase Species

Absolute Tolerance for Surface Species

Relative Tolerance for Surface Species

2009 Reaction Design

Getting Started with CHEMKIN-CFD

CHEMKIN-CFD for FLUENT

Summary of Advanced CHEMKIN-CFD Parameters