Chemkincfd Fluent12 PDF

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 Design’s 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
2 Getting Started with CHEMKIN-CFD ....................................................................................................................13

2.1 Enabling the CHEMKIN-CFD Module in FLUENT..................................................................................14
2.2 Setting Initial Conditions for Combustion Problems ...............................................................................17
2.3 Turbulence-Chemistry Interactions Models and CHEMKIN-CFD ........................................................17
2.4 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
2.5 User Programming.......................................................................................................................................25
2.6 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
3 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
3.2 Locating Other Chemical Reaction Mechanisms....................................................................................35
A Background Details for Working with Reaction Mechanisms .......................................................................37

A.1 Thermodynamic Property Database .........................................................................................................37
A.2 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
A.3 Surface Kinetics Input .................................................................................................................................57
A.3.1 Material Declaration ...................................................................................................................58
A.3.2 Site Data ......................................................................................................................................58
A.3.3 Bulk Data .....................................................................................................................................60
CFD-FLU-20091-0905-UG-1 3 May 2009

CHEMKIN-CFD for FLUENT Table of Contents
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
A.4 TRANSPORT Input ..........................................................................................................................................76
B 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
B.2 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
C Nomenclature ..........................................................................................................................................................111
C.1 Latin Equation Symbols ............................................................................................................................111
C.2 Greek Equation Symbols..........................................................................................................................116
C.3 Subscript Equation Symbols ....................................................................................................................118
Index ..........................................................................................................................................................................121
© 2009 Reaction Design 4 CFD-FLU-20091-0905-UG-1

Contents
List of Tables
2-1 Summary of Basic CHEMKIN-CFD Parameters ..............................................................................................................20
2-2 Summary of Advanced CHEMKIN-CFD Parameters .......................................................................................................21
2-3 Diagnostic Output Files Created During a CHEMKIN-CFD Run ......................................................................................26
2-4 Error Messages that May Be Printed to the FLUENT GUI ............................................................................................28
2-5 Other (non-License) Error Messages in KINetics-log.txt ...............................................................................................31
A-1 Summary of the Rules for Thermodynamic Data ..........................................................................................................39
A-2 Summary of the Rules for Element Data .......................................................................................................................43
A-3 Summary of the Rules for Species Data .......................................................................................................................44
A-4 Reaction Data Criteria ...................................................................................................................................................47
A-5 Summary of the Rules for Gas-phase Reaction Data ...................................................................................................49
A-6 Summary of the Rules for Gas-phase Auxiliary Information Data .................................................................................55
A-7 Error Checks .................................................................................................................................................................56
A-8 Summary of the Rules for Site Data ..............................................................................................................................60
A-9 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 Latin Symbols ..............................................................................................................................................................111
C-2 Greek Symbols ............................................................................................................................................................116
CFD-FLU-20091-0905-UG-1 5 May 2009

CHEMKIN-CFD for FLUENT List of Tables
C-3 Subscript Symbols.......................................................................................................................................................118

Contents
List of Figures
2-1 FLUENT Graphical User Interface ................................................................................................................................14
2-2 FLUENT Species Model Panel......................................................................................................................................15
2-3 FLUENT Import Chemkin Panel ....................................................................................................................................15
2-4 Text User Interface Commands for Changing CHEMKIN-CFD Parameters ....................................................................19
A-1 Excerpts from the Chemkin therm.dat Thermodynamic Database File .........................................................................39
A-2 Equivalent Ways to Describe Element Information .......................................................................................................43
A-3 Equivalent Ways to Describe Species Information........................................................................................................44
A-4 Examples of Reaction Data. ..........................................................................................................................................48
A-5 Examples of Gas-phase Auxiliary Information Data ......................................................................................................54
A-6 Examples of Site Data ...................................................................................................................................................59
A-7 Examples of Bulk Data ..................................................................................................................................................62
A-8 Examples of Surface Reaction Data .............................................................................................................................66
A-9 Examples of Auxiliary Surface Reaction Data ...............................................................................................................72
A-10 Surface Kinetics Input File using Multiple Materials ......................................................................................................75
B-1 Example Reaction for Adsorption, Using Atomic Site Formalism .................................................................................93
B-2 Example Reaction for Desorption, Using Atomic Site Formalism .................................................................................94
B-3 Example Reaction for Adsorption, Using Open Site Formalism ....................................................................................94
B-4 Illustration of an Adsorption Reaction using the Atomic Site Formalism .......................................................................95
B-5 Illustration of an Adsorption Reaction using the Open Site Formalism .........................................................................95
B-6 Examples of reactions with such non-integer coefficients ...........................................................................................100
B-7 Example of Sticking-coefficient Reaction with No Surface Species ............................................................................104
CFD-FLU-20091-0905-UG-1 7 May 2009

CHEMKIN-CFD for FLUENT List of Figures
B-8 Example of Sticking-coefficient Reaction with a Surface Site .....................................................................................104
B-9 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

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.
CFD-FLU-20091-0905-UG-1 9 May 2009

CHEMKIN-CFD for FLUENT 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 Information Resources

Reaction Design user documentation and tutorials are provided to assist you.
1.1.1 Contents of this Manual

This manual serves as a user guide for the fully coupled CHEMKIN-CFD for FLUENT
package, where Reaction Design’s 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.

Introduction CHEMKIN-CFD for FLUENT
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 FLUENT-
compatible 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
CFD-FLU-20091-0905-UG-1 11 © 2009 Reaction Design

CHEMKIN-CFD for FLUENT Introduction

2 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 user’s 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 user’s own case), allowed the problem to iterate to
a specified end time or steady-state, and verified the results through post-
processing.
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.
CFD-FLU-20091-0905-UG-1 13 May 2009

CHEMKIN-CFD for FLUENT 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.

Getting Started with CHEMKIN-CFD CHEMKIN-CFD for FLUENT
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 surface-
chemistry and transport-
property 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.

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
FLUENT’s multicomponent transport formulation, rather than the native CHEMKIN form.

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 CHEMKIN-

CFD
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.

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 FLUENT’s 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.

Figure 2-4 Text User Interface Commands for Changing CHEMKIN-CFD Parameters

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
Default
Parameter Usage
Value
Print Level Controls the level of diagnostic printing to the CHEMKIN-CFD diagnostic 1
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.
Absolute Tolerance Controls the smallest value of a species mass fraction that will be 1.E-8
for Gas-phase tracked by the CHEMKIN-CFD solver convergence algorithm. This
Species 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.
Relative Tolerance Controls the accuracy to which gas species mass fractions are 1.E-4
for Gas-phase resolved. Roughly this parameter controls the number of significant
Species 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.
Absolute Tolerance Controls the smallest value of a surface species site fraction that will 1.E-8
for Surface Species 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.
Relative Tolerance Controls the accuracy to which surface species site fractions are 1.E-4
for Surface Species 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.

Table 2-2 Summary of Advanced CHEMKIN-CFD Parameters
Default
Parameter Usage
Value
Pseudo Time- Determines which solver to use during pseudo time-stepping used to 1
stepping Solver improve the initial guess in a cell for steady-state simulations. By
Option 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 time-
stepping 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.
Pseudo Time- This option is only relevant if the Pseudo Time-stepping Solver Option 1.E-6
stepping Size is set to 1 (the default setting). This controls the time interval for time-
stepping when time-stepping is used to assist a steady-state [seconds]
calculation. See Section 2.4.1 for more information. We recommend
a value of 1.E-4 seconds for combustion problems.
Maximum Pseudo This parameter controls how many iterations between time-stepping 1
Time-stepping and steady-state solution attempts can be tried before the solver gives
Attempts 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 Maximum pseudo time-step value for time integration during steady- 1.E-2
Allowed state solution. This value is relevant to steady-state simulations only.
[seconds]
Minimum Time Step Minimum pseudo time-step value for time integration during steady- 1.E-10
Allowed state solution. This value is relevant to steady-state simulations only.
[seconds]
Initial Time Step for Initial time-step value for use in time integration. By default, the solver 0 (i.e., not
Solver will automatically choose an appropriate initial time step, which is the specified)
recommended approach. In rare cases, however, control of initial time
step value may improve convergence behavior. [seconds]
Upper Bound for Sets the upper bounds for the gas-phase species mass fractions 1.01
Gas-species Mass during steady-state solution. In some cases, it may help convergence
Fraction to allow species to go slightly over the physical bounds during interim
steady-state iterations rather than forcing the bounds to be one.

Table 2-2 Summary of Advanced CHEMKIN-CFD Parameters (Continued)
Default
Parameter Usage
Value
Lower Bound for Sets the lower bounds for the gas-phase species mass fractions during -1.E-12
Gas-species Mass steady-state solution. In some cases, it may help convergence to allow
Fraction 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.
Upper Bound for Sets the upper bounds for the surface species site fractions during 1.1
Surface Site steady-state solution. In some cases, it may help convergence to allow
Fraction species to go slightly over the physical bounds during interim steady-
state iterations rather than forcing the bounds to be one.
Lower Bound for Sets the lower bounds for the surface species site fractions during -1.E-4
Surface Site steady-state solution. In some cases, it may help convergence to allow
Fraction species to go slightly negative during interim steady-state iterations
rather than forcing the bounds to be zero.
Small Positive This value will be used to substitute any non-positive species fractions 1.E-12
Value to Replace during interim steady-state iterations. In some cases, setting this to a
Negative Species very small positive number may aid convergence for the steady-state
Fractions solver.
Enter Auxiliary A filename in the local working directory containing auxiliary parameter ““
Input File 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 CHEMKIN-
CFD module.
Enter Arbitrary Parameter string for indicating a parameter that has not yet been ““
String 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 associated with the parameter indicated by the Arbitrary String 0
Value 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 units
updates by Reaction Design of the CHEMKIN-CFD module. depend on
parameter
string

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 Newton-
iteration.method.

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.

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 gas-
phase 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 user-

routine 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 pre-
processing or run steps. In addition, error messages may be written in the FLUENT
Graphical User Interface window during run-time processing.

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 When File Is Created Contents Description
<gas_chemistry>.out Always created during pre- This file echoes back the gas-phase chemistry
processing, upon saving the reaction set, species names, and elements in
CHEMKIN mechanism formatted text. In addition, detailed error
definition. messages are contained in this file in case an
error is encountered while processing the gas-
phase chemistry input file and gas-phase
thermodynamic data.
chem.asc Always created during pre- A “Linking File” used to transfer the pre-
processing, upon saving the processed information to the CHEMKIN-CFD
CHEMKIN mechanism module at run-time. This file is typically not
definition. viewed by the user, but may occasionally be
requested by Technical Support during problem
diagnosis.
<surface_chemistry>.out Created during pre- This file echoes back the surface chemistry
processing, only if surface reaction set and the surface phase and species
chemistry box is checked in names. In addition, detailed error messages are
CHEMKIN mechanism contained in this file in case an error is
definition. encountered while processing the surface
chemistry input file and surface-species
thermodynamic data.
surf.asc Created during pre- A “Linking File” used to transfer the pre-
processing, only if surface processed information to the CHEMKIN-CFD
chemistry box is checked in module at run-time. This file is typically not
CHEMKIN mechanism viewed by the user, but may occasionally be
definition. requested by Technical Support during problem
diagnosis.
<transport_data>.out Created during pre- This file echoes back the transport-data fitting
processing, only if transport- coefficients in formatted text. In addition, detailed
property box is checked in error messages are contained in this file in case
CHEMKIN mechanism an error is encountered while processing the gas-
definition. phase transport data.

Table 2-3 Diagnostic Output Files Created During a CHEMKIN-CFD Run (Continued)
Filename When File Is Created Contents Description
tran.asc Created during pre- A “Linking File” used to transfer the pre-
processing, only if transport- processed information to the CHEMKIN-CFD
property box is checked in module at run-time. This file is typically not
CHEMKIN mechanism viewed by the user, but may occasionally be
definition. requested by Technical Support during problem
diagnosis.
KINetics-log.txt Created when the simulation Messages are written to this file that record the
run is initiated. 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>_ Created for Monitor Cells Includes debug information, including the actual
<iteration_number>.DBG (see Section 2.4.2) at every input sent into the CHEMKIN-CFD module by
iteration or time-step, any FLUENT for the particular cell and iteration. This
time that the Print Level information may be requested by Reaction
(Table 2-1) is >0. Also Design Technical Support when diagnosing cell
created any time that a cell failures.
fails in the CHEMKIN-CFD
solver and the Print Level is
>0.
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.

Table 2-4 Error Messages that May Be Printed to the FLUENT GUI
Error Message Recommended Action
Cannot read gas-phase chemistry input file. Verify the filename and file path for the gas-phase
chemistry input file in the CHEMKIN Import panel and re-
import.
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 Check the <gas_chemistry>.out file in the working
file during gas-phase pre-processing. directory for error messages.
file during surface pre-processing. directory for error messages.
file during transport pre-processing. directory for error messages.
Cannot read surface chemistry linking data file Check the <surface_chemistry>.out file in the working
during surface pre-processing. directory for error messages.
Cannot read transport properties linking data file Check the <transport_data>.out file in the working
during transport pre-processing. directory for error messages.
Cannot write gas-phase 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 surface chemistry output file. Check file permissions on working directory and make
Cannot write transport properties output file. Check file permissions on working directory and make
sure that there is only one FCHEMKIN-CFD for FLUENT
Cannot write gas-phase chemistry linking data Check file permissions on working directory and make
file. sure that there is only one CHEMKIN-CFD for FLUENT
Cannot write surface chemistry linking data file. Check file permissions on working directory and make

Table 2-4 Error Messages that May Be Printed to the FLUENT GUI (Continued)
Cannot write transport properties linking data Check file permissions on working directory and make
file. sure that there is only one CHEMKIN-CFD for FLUENT
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
Thermodynamic data file is NULL. Verify thermodynamic-data file path in the CHEMKIN
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 Check the <gas_chemistry>.out file in the working

chemistry mechanism. directory for error messages.
Failure in pre-processing of surface chemistry Check the <surface_chemistry>.out file in the working
mechanism. directory for error messages.
Failure in pre-processing of transport Check the <transport_data>.out file in the working

properties. directory for error messages.
Failure in CHEMKIN Gas-phase 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 Surface library call. This is likely due to an overflow or invalid number being
information.
Failure in CHEMKIN Transport library call. This is likely due to an overflow or invalid number being
information.

Table 2-4 Error Messages that May Be Printed to the FLUENT GUI (Continued)
Need to run CHEMKIN-CFD PreProcess first. 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 Check the KINetics-log.txt file in the working directory for
output file for details. error messages. See Section 2.6.2 for more information.
License error in CHEMKIN-CFD model, see Check the KINetics-log.txt file in the working directory for
diagnostic output file for details. 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.

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
FAILURE INITIALIZING SETTINGS FOR THE Most likely suggests an error in setting the
KINetics STEADY-STATE GAS-PHASE CHEMISTRY convergence criteria (i.e. absolute and relative
SOLVER tolerance) and the pseudo-steady-state time stepping
parameters. Check that the user-provided values are
reasonable.
WARNING: Exceeded allowed time-stepping Indicates that a convergence problem was

intervals in cell encountered during steady-state solution, where time-
stepping 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 steady-
state 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 Indicates that the problem is difficult to converge so
steps without convergence in this cell; 500 more that the transient solver is taking extra steps.
steps will be allowed 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.

Table 2-5 Other (non-License) Error Messages in KINetics-log.txt (Continued)
KINETICS ERROR: Problem getting species Indicates a possible error in the pre-processing of the
names; Check that the CHEMKIN files have been gas-phase chemistry input file. Check the
processed correctly <gas_chemistry>.out file for error messages.
KINETICS ERROR: Problem getting surface Indicates a possible error in the pre-processing of the
chemistry info; Check that the CHEMKIN files have surface chemistry input file. Check the
been processed correctly <surface_chemistry>.out file for error messages.
DASPK:... 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 Design’s 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.

3 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:
3 A file containing thermochemical data for the chemical species of interest.

3 A file containing a description of the reactions occurring in the gas phase.
3 A file containing a description of the reactions occurring at the gas-surface
interface or on the surface. (Optional)
3 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).
CFD-FLU-20091-0905-UG-1 33 May 2009

CHEMKIN-CFD for FLUENT 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 sub-
mechanism is the same as the "H2_mech" mechanism, above. The NOx sub-
mechanism is based on the recent study by the Glarborg group5.
1. Smith, G. P., D. M. Golden, et al. "GRI-Mech 3.0." 2008, from http://www.me.berke-

ley.edu/gri_mech/.
2. Naik, C. V., K. V. Puduppakkam, et al. (2008). Modeling Combustion Characteristics of Com-
ponents of Model-Biodiesel at High Temperatures. WSS/CI Spring 2008 Meeting, Los Angeles,
CA.
3. CHEMKIN-MFC 3.0, Reaction Design: San Diego, 2008.
4. Li, J., Z. Zhao, et al. (2007). "A Comprehensive Kinetic Mechanism for CO, CH2O, and
CH3OH Combustion." Int. J. Chem. Kinet. 39: 109-136.
5. Rasmussen, C. L., A. E. Rasmussen, et al. (2008). "Sensitizing Effects of NOx on CH4 Oxida-
tion at High Pressure." Comb. Flame 154(3): 529-545.

Chemical Reaction Mechanisms CHEMKIN-CFD for FLUENT
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.

CHEMKIN-CFD for FLUENT Chapter 3: Chemical Reaction Mechanisms

A Background Details for Working with

Reaction Mechanisms
This appendix provides guidance on creating and formatting the thermodynamic, gas-
phase chemistry, surface chemistry, and transport input data, which may be needed in
running a FLUENT/CHEMKIN-CFD problem:
Thermodynamic Property Database page 37

Gas-phase Kinetics Input page 41
Surface Kinetics Input page 57
Transport Input 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.
CFD-FLU-20091-0905-UG-1 37 May 2009

CHEMKIN-CFD for FLUENT 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
o
C pk
-------- = a 1k + a 2k T k + a 3k T k 2 + a 4k T k 3 + a 5k T k 4
R
Equation A-2
o
Hk a 2k a 3k 2 a 4k 3 a 5k 4 a 6k
--------
- = a 1k + ------
- T k + ------
- T + ------- T k + ------- T k + -------
RT k 2 3 k 4 5 Tk
Equation A-3
o
S a 3k 2 a 4k 3 a 5k 4
----k- = a 1k ln T k + a 2k T k + ------
- T + ------- T k + ------- T k + a 7k
R 2 k 3 4
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.

Background Details for Working with Reaction Mechanisms CHEMKIN-CFD for FLUENT
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 1
0.01913678E+03 0.08578044E-01-0.08882060E-05-0.03574819E-08 0.06605142E-12 2
-0.06560876E+06-0.08432507E+03-0.04662286E+02 0.06091547E+00-0.04710536E-03 3
0.01968843E-06-0.03563271E-10-0.05665403E+06 0.04525264E+03 4
AL 62987AL 1 G 0300.00 5000.00 0600.00 1
0.02559589E+02-0.10632239E-03 0.07202828E-06-0.02121105E-09 0.02289429E-13 2
0.03890214E+06 0.05234522E+02 0.02736825E+02-0.05912374E-02-0.04033937E-05 3
0.02322343E-07-0.01705599E-10 0.03886794E+06 0.04363879E+02 4
END
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 # Contents Format Column
1 THERMO (or THERMO ALL)a Free Any
2 Temperature ranges for 2 sets of coefficients: lowest 3F10.0 1 to 30

T, common T, and highest Tb

Table A-1 Summary of the Rules for Thermodynamic Data
Line # Contents Format Column
3 Species name (must start in Column 1) 18A1 1 to 18
Date (not used) 6A1 19 to 24
Atomic symbols and formula 4(2A1,I3) 25 to 44
Phase of species (S, L, or G for solid, liquid, or gas, A1 45

respectively)
Low temperature E10.0 46 to 55
High temperature E10.0 56 to 65
Common temperature (if needed, else blank) E8.0 66 to 73
Atomic symbols and formula (if needed, else blank) (2A1,I3) 74 to 78
The integer 1 I1 80
Atomic symbols and formula (if needed, else blank) 4(2A1,I3) 81 to 100
4 Coefficients a 1 through a 5 in Equation A-1 through 5(E15.8) 1 to 75

Equation A-3, for upper temperature interval
The integer 2 I1 80
5 Coefficients a 6 , a 7 for upper temperature interval, 5(E15.8) 1 to 75

and a 1 , a 2 , and a 3 for lower temperature interval
The integer 3 I1 80
6 Coefficients a 4 , a 5 , a 6 , a 7 for lower 5(E15.8) 1 to 60

temperature interval
The integer 4 I1 80
... Repeat lines 3 - 6 for each species
last 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.

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

mole) stored internally in the CHEMKIN-CFD module. For isotopes, a one- or two-
character 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.

Figure A-2 Equivalent Ways to Describe Element Information

ELEMENTS H D /2.014/ O N END
ELEM ! ELEM is equivalent to ELEMENTS

H
D / 2.014 /
O
N
END ! an END line is optional
ELEM H
ELEM D/2.014/
ELEM O
ELEM
Table A-2 summarizes the rules for element data.
Table A-2 Summary of the Rules for Element Data
Rule Description
1 The first element line must start with the word ELEMENTS (or ELEM).
2 Element or isotope names are either one- or two-character symbols.
3 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.
4 Each element or isotope should be declared only once; however, duplicated

element symbols will be ignored.
5 An element or isotope name may appear anywhere on the line.
6 Any number of element or isotope names may appear on a line, and more than
one line may be used.
7 Element or isotope names that appear on the same line must be separated by
at least one blank space.
8 An element or isotope name that begins on one line may not continue to the
next line.
9 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 There may be more than one ELEMENT statement.
11 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.

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 H2 O2 H O OH HO2 N2 N NO END
SPEC ! SPEC is equivalent to SPECIES

H2 O2
H O OH HO2 N2 N NO
END
SPEC H2
spec O2
The rules for species data are summarized in Table A-3.
Table A-3 Summary of the Rules for Species Data
Rule Description
1 Species data must start with the word SPECIES (or SPEC).
2 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 -.
3 Each species should be declared only once; however, duplicated species

symbols will be ignored.
4 Each species that subsequently appears in a reaction must be declared.
5 A species name may appear anywhere on the line.
6 Any number of species names may appear on a line, and more than one line
may be used.
7 Species named on the same line must be separated by at least one blank
space.
8 A species name that begins on one line may not continue to the next line.
9 There may be more than one SPECIES statement.

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

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 (lines 3 - 6 repeated) for at least all species named in
the species data
END
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 user-
supplied 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.

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 GAS-
PHASE 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

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 , β 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 β 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 CAL/MOLE
2 + O2 = 2OH 1.7E13 0 47780. ! Ref. 21
! H2 + O2 = OH + H 1.7E13 0 47780. ! same as previous reaction,
! commented to prevent a duplication error
H + O2 + M = HO2 + M 2.0E15 0.000 -870.
! H + O2 + M = HO2 2.0E15 0.000 -870.
! H + O2 = HO2 + M 2.0E15 0.000 -870.
OH+ + H + E = H2O 1.E19 0 0.0
O + HV = O(*) 1.3A5 0 0
0.5H2 + 0.5O2 = OH ! example of real coefficients
END ! END statement is optional;
! <eof> condition is equivalent

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 Description
1 The first reaction line must start with the word REACTIONS (or REAC), and may
include units definition(s).
2 The reaction description can begin anywhere on the line. All blank spaces,
except those between Arrhenius coefficients, are ignored.
3 Each reaction description must have =, <=> or => between the last reactant and
the first product.
4 Each reaction description must be contained on one line.
5 Three Arrhenius coefficients must appear in order ( A i , β 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 There cannot be more than six reactants or six products in a reaction.
7 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.
A.2.4.3.2 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

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 ∞ , β ∞ , and E ∞ ) for unimolecular fall-off reactions and
represent the low-pressure limit ( A o , β 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 high-
pressure 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 , β 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 ∞ , β ∞ , 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).

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.
A.2.4.3.4 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.
A.2.4.3.5 Landau-Teller Reactions

To specify Landau-Teller parameters, the keyword LT must be followed by two
parameters—the coefficients B i and C i from Equation B-31. The Arrhenius
parameters A i , β 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.2.4.3.6 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 , β 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.
A.2.4.3.7 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 υ ′ ki and υ ″ ki in
Equation B-4, for the species included in the auxiliary data.
A.2.4.3.8 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.
A.2.4.3.9 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.

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.

Figure A-5 Examples of Gas-phase Auxiliary Information Data

REACTIONS CAL/MOLE
HCO+M=H+CO+M 0.250E+15 0.000 16802.000 ! Warnatz
CO/1.87/ H2/1.87 CH4/2.81/ CO2/3./ H2O/5./
H+C2H4(+M)=C2H5(+M) 0.221E+14 0.000 2066.000 ! Michael

LOW / 6.369E27 -2.76 -54.0 / !Lindemann fall-off reaction
H2/2/ CO/2/ CO2/3/ H2O/5/ ! enhanced third-body efficiencies
CH3+CH3(+M)=C2H6(+M)9.03E16 -1.18 654.

LOW / 3.18E41 -7.03 2762 /
TROE / 0.6041 6927. 132. / ! TROE fall-off reaction, with 3 parameters
CH3+H(+M)=CH4(+M)6.0E16 -1.0 0.0

LOW / 8.0E26 -3.0 0.0/
SRI / 0.45 797. 979. / ! SRI fall-off reaction
CH3+CH3(+M)=H + C2H5(+M)4.989E12 0.099 10600.0! Stewart

HIGH/ 3.80E-7 4.838 7710. / ! Chemically activated reaction
SRI / 1.641 4334 2725 / ! SRI pressure dependence
CH4+H=CH3+H2 1.25E14 0 1.190E4 ! Westbrook

REV / 4.80E12 0 1.143E4 /
! The following two reactions are acceptable duplicates:
H2+O2 = 2OH 1.7E13 0 47780

DUPLICATE
H2+O2 = 2OH 1.0E13 0 47000.
DUPLICATE
H2(1)+H2O(000)=H2(0)+H2O(001) 2.89E15 0 0
LT / -67 62.1/ ! Landau-Teller reaction
! The following is a Chebyshev polynomial rate description
C2H5 + O2 (+M) <=> C2H4E + HO2 (+M) 1.00E+00 .000 0. ! Bozzelli

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 0.117E+10 1.30 3626

FORD /H2O 1.1/
END !END line is optional

Table A-6 summarizes the rules for Auxiliary Information Data.
Table A-6 Summary of the Rules for Gas-phase Auxiliary Information Data
Rule Description
1 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).
2 A species may have only one enhanced third-body efficiency associated with it
in any one reaction.
3 Only one radiation wavelength may be declared in a reaction.
4 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 There cannot be more than ten enhanced third-bodies in a reaction.
6 Keyword declarations may appear anywhere on the line, in any order.
7 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.
8 Keyword declarations that appear on the same line must be separated by at

least one blank space.
9 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.
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.

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 Possible Errors
Element 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.

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).

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 1-
80 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 slash-
delimited 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.

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/ ! PLANAR SITE
ASH(V) ! FIRST SPECIES ON PLANE SITE
ASH2(V) ASH3(V) H(S) CH3(V) AS(V) AS2(V)/2/
V ! EMPTY PLANAR SITE
END ! AN END STATEMENT IS OPTIONAL
SITE / LEDGE / SDEN/1.66E-10/ ! LEDGE SITE
GACH(L) ! FIRST SPECIES ON LEDGE
DMG(L)/2/ ! THIS SPECIES OCCUPIES 2 SITES
L ! EMPTY LEDGE SITE
SITESDEN/1.0E-10/ GA(S) ! SITE WITH ONLY ONE SPECIES
! SITE NAME NOT INCLUDED

Table A-8 Summary of the Rules for Site Data
Rule Description
1 Site data must start with a line containing the word SITE, followed by an
optional slash-delimited name (i.e., SITE/name/).
2 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 A site species name may appear anywhere on the line.
9 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 There may be more than one set of SITE data.
12 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

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 Description
1 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/).
2 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.
3 Bulk and bulk species names are composed of up to sixteen upper- or lower-
case 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
(/).
4 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 A bulk species declaration may start anywhere on the line.
8 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 There may be more than one set of BULK data.

comments and are ignored.
12 BULK data are not required.

Figure A-7 Examples of Bulk Data

BULK / GA_RICH / GA2AS(1)/3.0/ GA3AS(1)/3.0/ END
!an END statement is optional
BULK / GA_RICH /
GA2AS(1)/3.0/
GA3AS(1)/3.0/
GA2AS(1)/2.0/ !THIS NAME IS A DUPLICATE AND WILL BE IGNORED
BULK AS(B) !BULK PHASE WITH NO NAME SUPPLIED
!ONLY ONE BULK SPECIES AND NO DENSITY SUPPLIED
END
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

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
β 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).

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 Motz-
Wise 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.

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 , β 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
A i are cgs (cm, sec, K, mole), the exact units depending on the order of the reaction. The
factor β i is dimensionless. The default units for the activation energies are cal/mole.
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.

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 Description
1 The first reaction line must start with the word REACTIONS (or REAC), and may
be followed by units definition(s), the word MWOFF.
2 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 sticking-
coefficient 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.
4 The reaction description can begin anywhere on this line. All blank spaces,
except those separating the Arrhenius coefficients, are ignored.
5 Each reaction description must have =, <=>, or => between the last reactant
and the first product.
6 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/.
7 Stoichiometric coefficients are represented by an integer or real number

preceding a species name. The default is to assume a stoichiometric coefficient
of 1.
8 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.

Table A-11 Summary of the Rules for Surface Reaction Data
Rule Description
9 Three Arrhenius coefficients must appear in order ( A i , β 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 There cannot be more than six reactants or six products in a reaction.
11 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.

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 , β 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.
A.3.5.3.2 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

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.
A.3.5.3.4 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.
A.3.5.3.5 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 υ ' ki and υ'' 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 υ ' ki and υ'' 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.
A.3.5.3.6 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 η ki , µ ki and ε 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.3.5.3.7 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
β 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 , β 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
β
equilibrium constant is defined as K = AT exp ( – H ⁄ RT ) , in parallel with the standard
expression for rate constants.

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/CHEMKIN-
CFD.
A.3.5.3.10 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.

Table A-12 Summary of the Rules for Surface Auxiliary Data
Rule Description
1 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 Auxiliary keyword declarations may appear anywhere on the line, in any order.
3 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.
4 Multiple keywords appearing on the same line must be separated by at least

one blank space.
5 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.
6 The keyword REV followed by three slash-delimited Arrhenius coefficients may

be used to specify the reverse rate parameters.
7 The auxiliary keyword DUPLICATE (or DUP) must follow every occurrence of a
duplicated reaction.
8 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.
9 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 η ki , µ ki and ε 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).

Table A-12 Summary of the Rules for Surface Auxiliary Data
Rule Description
12 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).

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./
CL + SICL(S) <=> CL2 + SI(S) 0.1 1.1 20.
DUPLICATE STICK
RORD /SI(S) 0/
CL + SICL(S) <=> CL2 + SI(S) 1.4E11 0.0 15.
DUPLICATE COV/SICL(S) -1.2 0.5 32./ FORD/CL+ 1.0/
CL* => CL 1.0 0.0 0.
STICK MWOFF
E + CL+ + SICL3(S) + SI(B) => SICL4 + SI(S) 0.50 0.0 0.
BOHM
ENRGDEP/1. 0.5 1.0/ UNITS/EVOLT/
E + CL+ + #SICL3(S) + #SI(B) + SICL(S) &
=> SICL2(S) + #SICL2 + #SICL(S) 0.50 0.0 0.0
BOHM
YIELD/0.0712 1.21 0.5 1.0/ UNITS/EVOLT/
E + CL2+ + SICL3(S) + SI(B) => SICL4 + SICL(S) 0.50 0.0 0.0
FORD/ CL2+ 2.43/
A + B => C + D 7.9E13 0. 56000.
LANG /A 3.6308E+36 0.0 -7.36 2./
LHDE /2/
LHNU /A C/
LHNU /A A/
LHPR /atm/
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 pre-
exponential factors consistent with cm, molecules, sec and K. The program converts
the user input activation energies accordingly.

However, it is worthwhile to state explicitly the conversion for the Arrhenius pre-
exponential constant. In converting from “molecules” to “moles”
Equation A-4
n–1
A i ( moles ) = A i ( molecules ) × ( N A )
where N A is the Avogadro number, and
Equation A-5
K s(N s)
l l
n = ∑ υ ' ki
k=1
Note that the υ ' 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:
Site and Bulk A duplicated species symbol (name) is not considered a fatal error,
Species Data 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 Thermodynamic data are format sensitive and therefore provide

Data possibilities for error if not formatted exactly as described by
Table A-1.

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 An unknown or misspelled keyword occurs.

Data 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 gas-

phase 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.

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

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 transport-
property 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 ε ⁄ k B in Kelvins,
the Lennard-Jones collision diameter σ in Angstroms, the dipole moment µ in
Debyes, the polarizability α 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 ε ⁄ k B in Kelvins.
3. The Lennard-Jones collision diameter σ in Angstroms.
4. The dipole moment µ in Debye.
A Debye is 10-18cm3/2erg1/2.
5. The polarizability α in cubic Angstroms.

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 Geometry ε ⁄ kB σ µ α Z rot.
Al2Me6 2 471. 6.71 0.0 0.0 1.0
AlMe3 2 471. 5.30 0.0 0.0 1.0
AR 0 136.500 3.330 0.000 0.000 0.000
AR* 0 136.500 3.330 0.000 0.000 0.000


B 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 FLUENT’s
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
∑ υ ′ki χk ⇔ ∑ υ ″ki χk ( i = 1 ,…, I )

k=1 k=1
The stoichiometric coefficients υ ki are integer numbers and χ k is the chemical

symbol for the kth species. The superscript ′ indicates forward stoichiometric
coefficients, while ″ indicates reverse stoichiometric coefficients. Normally, an
elementary reaction involves only three or four species; hence the υ 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 non-
integers.
CFD-FLU-20091-0905-UG-1 79 May 2009

CHEMKIN-CFD for FLUENT Chapter B: Theoretical Background
·
The production rate ω k of the kth species can be written as a summation of the rate-
of-progress variables for all reactions involving the kth species
Equation B-2
I
·
ωk = ∑ υki qi ( k = 1 ,…, K )
i=1
where
Equation B-3
υ ki = υ ″ ki – υ ′ 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 K
υ ′ ki υ ″ ki
q i = k fi ∏ [ X k ] – k ri ∏ [ X k ]
k=1 k=1
where [ X k ] is the molar concentration of the kth 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
β –Ei
k fi = A i T i exp ⎛ ---------⎞
⎝ R c T⎠
where the pre-exponential factor A i , the temperature exponent β i , and the activation
energy E i are specified. These three parameters are required input for each reaction.

Theoretical Background CHEMKIN-CFD for FLUENT
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
∑υ ki
P atm k = 1
K ci = K pi ⎛ ----------⎞
⎝ RT ⎠
The equilibrium constants K pi are obtained with the relationship
Equation B-8
o o
⎛ ∆ Si ∆ Hi ⎞
K pi = exp ⎜ --------- – ----------⎟
⎝ R RT ⎠
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.)

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 R ki
q i = k fi ∏ [ X k ] – k ri ∏ [ X k ]
k=1 k=1
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 = υ ′ ki
and
Equation B-11
R ki = υ″ 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-of-
progress variable is different from Equation B-4 by the first factor in the equation:

Equation B-12
⎛ K ⎞⎛ K K ⎞
⎜ ⎟ ⎜ υ ′ υ ″ ki⎟
q i = ∑ ( a ki ) [ X k ] k fi ∏ [ X k ] – k ri ∏ [ X k ]
ki
⎜ ⎟⎜ ⎟
⎝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 pressure-
dependent reaction-rate formulations. These include unimolecular/recombination fall-
off 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

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 high-
and low-pressure limiting cases, and these are blended to produce a pressure-
dependent rate expression. In Arrhenius form, the parameters are given for the high-
pressure limit k ∞ and the low-pressure limit k 0 as follows:
Equation B-14
β0
k 0 = A 0 T exp ( – E 0 ⁄ R c T )
Equation B-15
β∞
k∞ = A∞ T exp ( – E ∞ ⁄ R c T )
The rate constant at any pressure is then taken to be
Equation B-16
Pr
k = k ∞ ⎛ ---------------⎞ F
⎝ 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).

Equation B-18
log P r + c 2 –1
log F = 1 + ---------------------------------------- log F cent
n – d ( log P r + c )
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 – α )exp ( – T ⁄ T ) + α exp ( – T ⁄ T ) + exp ( – T ⁄ T)
*** * **
The four parameters α , 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
X e
F = d aexp ⎛ ------⎞ + exp ⎛ ------⎞
–b –T
T
⎝ T⎠ ⎝ c⎠
where
Equation B-24
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).

In addition to the six Arrhenius parameters—three each for the low-pressure limit k 0
and high-pressure limit k ∞ expressions—the 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 weak-
collision 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
k = k 0 ⎛ ---------------⎞ F
1
⎝ 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.

For a given reaction, then, the user would supply rate parameters
βj
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 logk as a function of logP
(natural logarithms). For P between P i and P i + i, k , k is obtained using
Equation B-26.
Equation B-26
logP – logP i
logk = logk i + ( logk i + l – logk i ) --------------------------------------
logP i + l – logP 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, multiple-
channel 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).

Troe, and SRI forms, although accurate for representing the falloff behavior of single-
well 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
–1 –1 –1
2T – T min – T max
T̃ = --------------------------------------------
–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.

Equation B-28
2 log P – log P min – log P max

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
log k (T˜ ,P˜ ) ≈ ∑ ∑ a nm ϕ n ( T˜ ) ϕ m ( P˜ )

n = 1m = 1
where the Chebyshev polynomials of the first kind of degree n – 1 are given by
Equation B-30
–1
ϕ ( 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
rate coefficient data points, k (T̃,P̃) , computed from a detailed theory such as the Rice-
Ramsperger-Kassel-Marcus (RRKM) theory. To ensure the approximation is uniform
over the desired domain, the computed rate coefficient data must be on the Gauss-
Chebyshev grid. For example, if the computed rate coefficient data is on a Gauss-
Chebyshev grid, its coordinates, T̃ i and P̃ j , must be the roots of a high-order
Chebyshev polynomial of the first kind given by
Equation B-31
T̃ i = cos ⎛ -------------- π⎞
2i – 1
⎝ 2d T ⎠
Equation B-32
P̃ j = cos ⎛ -------------- π⎞
2j – 1
⎝ 2d P ⎠
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 .

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
⎛ Bi Ci ⎞
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
β ⎛ –Ei Bi Ci ⎞
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 β 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.

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

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
o
µ k ( T, P, X ) = µ k ( T ) + RT ln ( a k ( T, P, X ) )
o
where µ 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.

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).

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) )

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

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
phase phase (n) .
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

Equation B-37
f l
[ Xk ] = Yk ρ ⁄ Wk ( k = K g, …, K g )
where the Y k are the mass fractions, ρ 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
∑
f l
Zk ( n ) = 1 ( n = N s, …, N s )
k = K s( n)
f
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 ) Γn ⁄ σk ( n )
where Γ n is the density of sites of phase n (in mole/cm2) and σ 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
f l
[ 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

Equation B-41
K K
∑ υ 'ki χk ⇔ ∑ υ ''ki χk ( i = 1, …, I )
k=1 k=1
The stoichiometric coefficients for elementary reactions υ ki are integers and χ k is the
chemical symbol for the kth species. Usually, an elementary reaction involves only
three or four species; hence the υ ki matrix is quite sparse for a large set of reactions.
Global reactions are sometimes stated with non-integer stoichiometric coefficients. CHEMKIN-
CFD can accommodate non-integer stoichiometric coefficients.
The net production rate s· k (in mole/cm2/sec) for each of the K species (regardless of
phase) is the sum of the rate-of-production for all reactions involving the kth species
Equation B-42
I
s· k = ∑ υki qi ( k = 1, …, K )
i=1
where
Equation B-43
υ ki = υ '' ki – υ ' 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 K
υ' ki υ'' ki
q i = k fi ∏ [ X k ] – k ri ∏ [ X k ]
k=1 k=1
·
The production rate Γ n (in mole/cm2/sec) for each surface phase is
Equation B-45
I
·
∑ ∆σ ( n, i )qi
f l
Γn = ( n = N s, …, N s )
i=1
where

Equation B-46
Ks ( n )
l
∆σ ( n, i ) = ∑ υ ki σ k ( n )
k = Ks ( n )
f
The term ∆σ ( 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
β –Ei
k fi = A i T i exp ⎛⎝ ---------⎞⎠
Rc T
where the pre-exponential factor A i , the temperature exponent β 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.

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
l
Kg K s(n)
∑υ ki ∑υ f
ki
l k = K s(n)
K s( n)
k=1 l
P atm N
–υ
= ⎛ ----------⎞
s
∏ ∏
o
K ci (Γ n) σ k ki K pi
⎝ RT ⎠ f
k = K s( n)
f
n=Ns
o
where P atm denotes a pressure of 1 atm, and Γ 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
o o
⎛ ∆S i ∆H i ⎞
K pi = exp ⎜ --------- – ----------⎟
⎝ R RT ⎠
B.2.4.1 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 υ ' ki and υ '' ki defined as real numbers instead of integers. The GAS-
PHASE KINETICS and SURFACE KINETICS Pre-processors automatically allow real
coefficients for reactions without requiring any special flags or keywords.

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 R ki
q i = k fi ∏ [ X k ] – k ri ∏ [ X k ]
k=1 k=1
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 = υ ' ki
Equation B-53
R ki = υ '' ki
if an order-change parameter is not given for species k participating in that reaction.

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
υ' ki
∏ [ Xk ] K
k ri υ' ki – υ'' ki
∏ [ Xk ]
k=1
------ = ---------------------------
- =
k fi K
υ'' ki
∏ [ Xk ]
k=1
k=1
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 = υ' ki – υ'' 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
K s( N s)
l l
β –Ei η ki [ Z k ( n ) ] µ ⎛ – ε ki [ Z k ( n ) ]⎞
k fi = A i T i exp ⎛ --------⎞ ∏ 10 [ Z k ( n ) ] ki exp ⎜ ----------------------------⎟
⎝ RT ⎠ ⎝ RT ⎠
k = K s(N s)
f f

where the three coverage parameters are η ki , µ ki , and ε 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 µ 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 + ∑ η ki [ Z k ( n ) ]
k = K s(N s)
f f
and the activation energy is a function of the coverage
Equation B-58
Ks ( Ns )
l l
E = Ei + ∑ ε ki [ Z k ( n ) ]
k = Ks ( Ns )
f f
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 γ i is defined as a probability, it must lie between 0 and 1 to make physical sense.
Therefore, CHEMKIN-CFD checks the value of γ i , and an unphysical sticking coefficient greater
than 1 is changed to the value 1.

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
b –ci ⁄ Rc T
γ i = min [ 1, a i T i e ]
In this case, a i and b i are unitless and c i has units compatible with R c . CHEMKIN-
CFD 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 γ 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 γ 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 γ 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 γ 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

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 γ i to the usual mass-action

kinetic rate constants there is the relation
Equation B-60
υ ' ji
∏ σj
k fi = γ i j------------------
=1 RT -
- -------------
m 2πW
( Γ tot ) k
where R is the universal gas constant, W k is the molecular weight of the gas-phase
species, Γ 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
Γ 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, σ j is the number of sites that the
surface species occupies, and υ 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

Equation B-61
υ ' ji
γi
∏ σj
k fi = ⎛ -------------------⎞ j------------------
=1 RT -
- -------------
⎝ 1 – γ i ⁄ 2⎠ m 2πW
(Γ ) tot k
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 co-
adsorb 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)

Figure B-11 Langmuir-Hinshelwood Single Overall Reaction
A+B→C+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 mass-
action 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
β
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′ [ X A ] [ X B ]
q = ---------------------------------------------------------------------------------------------------------------2-
( 1 + KA [ XA ] + KB [ XB ] + KC [ XC ] + KD [ XD ] )
The generalized form of the above expression is:
Equation B-64
νi
∏ [ Xi ]
i
q = k′ ---------------------------------------
-
⎛ ⎞2
⎜ 1 + ∑ K i [ X ] i⎟
⎝ i
⎠

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
li
∏ [ Xi ]
i
q = k′ -------------------------------------------
-
⎛ n i⎞
m
⎜ 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 ( ν 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+B→C

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′ [ X A ] [ X B ]
q = ----------------------------------------------------------
( 1 + KA [ XA ] + KC [ XC ] )
The generalized form of this is:
Equation B-68
νi
∏ [ 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.


C Nomenclature
C.1 Latin Equation Symbols

The table below shows the conventions used in this document for latin symbols.
Table C-1 Latin Symbols
Symbol Description CGS Units
ai Pre-exponential factor in sticking coefficient expression none
ak Activity of the kth bulk-phase species none
a nk Coefficients of fits to thermodynamic data depends on n
a Mean specific Helmholtz free energy of a mixture ergs/g
Ai Pre-exponential factor in the rate constant of the i th depends on reaction

reaction
bi Temperature exponent in sticking-coefficient expression none
ci Activation energy in sticking-coefficient expression. By cal/mole

default, GAS-PHASE KINETICS INPUT and SURFACE KINETICS
input uses activation energies in calories instead of ergs.
c pk Specific heat capacity at constant pressure of the kth ergs/(g K)

species
c pk, int. Internal contribution to the mass specific heat of the kth ergs/(g K)
species
c pk, rot. Rotational contribution to the mass specific heat of the kth ergs/(g K)
species
CFD-FLU-20091-0905-UG-1 111 May 2009

CHEMKIN-CFD for FLUENT Chapter C: Nomenclature
Table C-1 Latin Symbols (Continued)
c vk Specific heat capacity at constant volume of the kth ergs/(g K)

species
cp Mean specific heat capacity at constant pressure ergs/(g K)
cv Mean specific heat capacity at constant volume ergs/(g K)
C pk Molar heat capacity at constant pressure of the kth ergs/(mole K)

species
o
C pk Standard state molar heat capacity at constant pressure of ergs/(mole K)
the species
C pk, trans. Translational contribution to the molar heat capacity of the ergs/(mole K)
kth species
C pk, vib. Vibrational contribution to the molar heat capacity of the ergs/(mole K)
kth species
C pk, rot. Rotational contribution to the molar heat capacity of the ergs/(mole K)
kth species
C vk Molar heat capacity at constant volume of the kth species ergs/(mole K)
Cp Mean molar heat capacity at constant pressure ergs/(mole K)
Cv Mean molar heat capacity at constant volume ergs/(mole K)
C· k Chemical creation rate of the kth species mole/(cm3 sec)
T
Dk Thermal diffusion coefficient of the kth species g/(cm sec)
D k, j Ordinary multicomponent diffusion coefficient of the cm2/sec

species k in species j
D kj Binary diffusion coefficient of species k in species j cm2/sec
D km Mixture-averaged diffusion coefficient of the kth species cm2/sec
D· k Chemical destruction rate of the kth species mole/(cm3 sec)

Nomenclature CHEMKIN-CFD for FLUENT
Ei Activation energy in the rate constant of the i th reaction. cal/mole

By default, GAS-PHASE KINETICS input and SURFACE
KINETICS input uses activation energies in calories instead
of ergs.
F ki Forward reaction-order specified for the kth species in i th none

reaction
hk Specific enthalpy of the kth species ergs/g
h Mean specific enthalpy of a mixture ergs/g
Hf Enthalpy of formation ergs/mole
o
Hk Standard state molar enthalpy of the kth species ergs/mole
Hk Molar enthalpy of the kth species ergs/mole
H Mean molar enthalpy of a mixture ergs/mole
I Total number of reactions none
kB Boltzmann Constant ergs/K
k fi Forward rate constant of the i th reaction depends on reaction
k ri Reverse rate constant of the i th reaction depends on reaction
K Total number of species none
Kb Total number of bulk species none
f
K b(n) Index of the first bulk-phase species in phase n none
l
K b(n) Index of the last bulk-phase species in phase n none
K ci Equilibrium constant in concentration units for the i th depends on reaction

reaction
Kg Total number of gas-phase species none
f
Kg Index of the first gas-phase species none
l
Kg Index of the last gas-phase species none

K pi Equilibrium constant in pressure units for the i th reaction depends on reaction
Ks Total number of surface species none
f
K s(n) Index of the first surface species in phase n none
l
K s(n) Index of the last surface species in phase n none
K phase Array containing the number of species in each phase none
m jk Reduced molecular mass for the collision g
mk Molecular mass of the kth species g
[M] Total molar concentration of a mixture mole/cm3
o
N Number of coefficients in polynomial fits to C p ⁄ R none
Total number of phases none
NA Avogadro’s number none
Nb Total number of bulk phases none
f
Nb Index of the first bulk phase none
l
Nb Index of the last bulk phase none
Ng Number of gas phases (always equal to 1) none
Ns Total number of surface site types (phases) none
f
Ns Index of first surface phase none
l
Ns Index of last surface phase none
P Pressure dynes/cm2
P atm Pressure of one standard atmosphere dynes/cm2
qi Rate of progress of the i th reaction. mole/(cm2 sec)
R Universal gas constant ergs/(mole K)

Rc Universal gas constant, in units consistent with activation [cal/(mole K)]*

energy
R ki Reverse reaction-order specified for the kth species in the none

i th reaction.
o
sk Standard state specific entropy of the kth species ergs/(g K)
s Mean specific entropy of a mixture ergs/(g K)
s· k Production rate of the kth species from surface reactions mole/(cm2 sec)
o
Sk Standard state molar entropy of the kth species ergs/(mole K)
Sk Molar entropy of the kth species ergs/(mole K)
S Mean molar entropy of a mixture ergs/(mole K)
T Temperature K
*
T ik Reduced temperature for the collision none
*
Tk Reduced temperature of the kth species none
To Ambient temperature K
Vk Diffusion velocity of the kth species cm/sec
Vk Ordinary diffusion velocity of the kth species cm/sec
W Mean molecular weight of a mixture g/mole
Wk Molecular weight of the kth species g/mole
Wk Thermal diffusion velocity of the kth species cm/sec
X Array of surface species mole fractions none
Xk Mole fraction of the kth species none
[ Xk ] Molar concentration of the kth species mole/cm3

Yk Mass fraction of the kth species none
Z Array of surface species site fractions none
Zk ( n ) Site fraction of the kth species on surface phase n 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
αi Parameter in mechanism none
αk Polarizability of the kth species Å3
*
αk Reduced polarizability of the kth species. none
α ki Enhanced third-body efficiency of the kth species in the i th none

reaction
βi Temperature exponent in the rate constant of the i th none

reaction
Γn Site density for surface phase n mole/cm2
o
Γn Initial site density for surface phase n mole/cm2
Γ tot Site density summed over all surface phases mole/cm2

·
Γn Production rate for surface phase n mole/(cm2 sec)
γi Sticking coefficient for the i th surface reaction none

Table C-2 Greek Symbols (Continued)

*
δ jk Reduced dipole moment of the kth species none
*
δk Effective reduced dipole moment for the collision none
ε Small number (e.g. 1.E-12) none
Emissivity none
ε jk Effective Lennard-Jones potential well depth for the ergs

collision
εk Lennard-Jones potential well depth for the kth species ergs
ε ki Coverage parameter [cal/mole K]*
η Mixture viscosity g/(cm sec)
ηk Pure species viscosity of the kth species g/(cm sec)
η ki Coverage parameter none
κ Bulk coefficient of viscosity g/(cm sec)
λ Thermal conductivity of the gas mixture ergs/(cm sec K)
λ0 Multicomponent thermal conductivity of the species ergs/(cm sec K)
λk Thermal conductivity of the kth species ergs/(cm sec K)
µ jk Effective dipole moment for the collision Debye
µk Dipole moment of the kth species Debye
*
µk Reduced dipole moment of the kth species none
µ ki Coverage parameter none
ξ ij Relaxation collision number none
ρ Mass density of a gas mixture g/cm3
ρk Mass density of the kth bulk species g/cm3

Table C-2 Greek Symbols (Continued)
σk Number of sites occupied by the kth species. none
Lennard-Jones diameter of the kth species Å
σ jk Effective Lennard-Jones diameter for the collision Å
υ ki Net stoichiometric coefficient of the kth species in the i th none

reaction; υ ki = υ ′ ki – υ ″ ki
υ ′ ki Stoichiometric coefficient of the kth reactant species in the none

i th reaction
υ ″ ki Stoichiometric coefficient of the kth product species in the none

i th reaction
χk Chemical symbol of the kth species none
Ω Collision integral none
ω· k Chemical production rate of the kth species due to gas- mole/(cm3 sec)
phase reactions
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
i Denotes reaction index, ionic species index, or inlet index.
k Species index

Table C-3 Subscript Symbols (Continued)
Symbol Description
n Phases index
Species index for a non-polar species
p Species index for a non-polar species


Index
Index
A error checks 74
examples of 72
activation energy 99, 103
keywords
activity 97
bulk species 92, 97 COV 68, 71, 102
gas species 93 DUP 68, 71, 74
site species 93 FORD 68, 71, 74, 101
adsorption 91, 93, 95, 106 LANG 72
arbitrary reaction order 68, 81, 101 LHDE 72
argon
methane combustion mechanism 34
LHNU 72
Arrhenius rate parameters 62, 63, 64, 65, 66, 67, 68, 71, 72, 74, LHPR 72
99, 107 MWOFF 66, 68, 72
atomic MWON 66, 68, 72
site formalism 94, 95 NONCON 74
auxiliary data 67, 68, 70 REV 67, 71, 99
gas-phase reactions
error checks 57
RORD 68, 71, 74, 101
examples of 54 STICK 65, 67, 68, 71
keywords UNITS 69, 71, 74
CHEB 51 summary of the rules 71
DUP 52
FORD 52 B
HIGH 50 balance
LT 51 elemental 94
MWOFF 64 site 94
MWON 64 blank
lines 59
PCHEB 51 spaces 64, 66, 71
PLOG 51 bulk
REV 52 data 60, 63
RLT 51 error checks 73
RORD 52 examples 62
TCHEB 51 summary of the rules for 61
density 73
UNITS 52 mixture 92, 93
Lindemann formulation of pressure dependence 50
names 61
summary of the rules for gas-phase reactions 55
phase 58, 60, 92, 96
surface reactions 64
CFD-FLU-20091-0905-UG-1 121 May 2009

CHEMKIN-CFD for FLUENT Index
species 58, 60, 92, 93, 96, 97 factor 105

activity 92, 97 Motz-Wise 64, 66, 68, 72
COV 68, 71, 72, 75, 102
coverage
C parameters 68, 71, 102, 103
capacity, heat 62
CHEB 51, 57
Chebyshev polynomial rate expressions 51, 88, 89 D
Gauss-Chebyshev grid 89 data
chemical auxiliary 64, 67, 68, 70
potential 92, 93 bulk 60, 63
reactions 63, 93 chemistry mechanisms
symbol 98 element 41
chemically activated bimolecular reactions 86 reaction 64
chemistry mechanisms 33 site 58, 63
gas-phase reaction 46 thermodynamic 62, 63
surface reaction 63 transport for gas-phase species 77
chemistry set. See chemistry mechanisms. default units 65, 69, 71
CHEMKIN 9, 16 delimiters 65, 74
CKUPROD 46 density
CKUPROG 53 bulk 73
coefficients 65 mass 61
non-integer stoichiometric 98, 100 sites of phase 97
sticking 64, 65, 67, 68, 72, 74, 103, 105 slash-delimited 58
stoichiometric 66, 68, 71, 73, 74, 98, 101, 105 standard-state site 58, 60
collision 104 surface site 100
diameter deposition 91
Lennard-Jones 76 desorption 91, 93, 106
frequency 105 diagnostic messages 73
number, rotational relaxation 77 dilution 92
comments 60, 61, 64, 67, 72 dipole moment 76
computational fluid dynamics 9 Directed Relational Graph method 34
concentration distribution, velocity
molar 96 non-Maxwellian 105
surface molar 97 dummy thermodynamic data 62
surface site 105 DUP 52, 56, 68, 71, 74
units 96, 100 duplicate reactions 52, 67
condensed-phase species 60
configuration, geometrical 76
conservation E
charge 91 efficiency, third body 49
elemental composition 91 element data 41
equations 96 error checks 56
mass 91 summary of the rules for 43
of mass and surface sites 91 elemental
constants balance 94
equilibrium 99, 100 composition 91
forward rate 99 elementary reactions 91, 100, 101
reverse rate 99 elements 59, 74, 94
surface reaction rate 103 ELEMENTS section of gas-phase chemistry file 42
universal gas 105 Eley-Rideal reactions 69, 72, 106
continuation energy
next line 66 activation 99, 103
correction Gibbs free 100

Index Chemkin-CFD for FLUENT Manual
of reaction 100 free energy

units 63, 69, 71 Gibbs 100
enthalpy 62 frequency, collision 105
entropy 62
equations
chemical potential 92 G
conservation 96 gas-phase 96
Greek symbols 116 mass density 97
Latin symbols 111 reaction data
subscript symbols 118 species 58, 60, 61, 63, 67, 74, 93, 96, 100, 105
equilibrium activity 93
behavior 102 indices 96
constants 99, 100, 107 gas-phase kinetics
error checks 73 input 41, 45, 46, 55, 63, 76, 81
auxiliary data, gas-phase reactions 57 pre-processor 59, 63, 74, 100
auxiliary data, surface reactions 74 Gauss-Chebyshev grid 89
bulk data 73 geometrical configuration 76
element data 56 Gibbs free energy 100
reaction data 56, 74 global rate expressions 98, 100
site data 73 Greek equation symbols 116
species data 56 grimech30_50spec 34
thermodynamic property data 56, 73
etching 91
ethane
H
chemistry mechanism 33 H2_mech 34
examples heat
auxiliary data, gas-phase reactions 54 capacity 62
auxiliary data, surface reactions 72 of formation 94
bulk data 62 Henry’s law 92
reaction data 48, 66 HIGH 50, 57
site data 59 hydrogen
exponent, temperature 72, 99 chemistry mechanism 33
expressions, rate hydrogen combustion mechanisms 34
global 100
reverse 67 I
ideal solution 97
F index
factor bulk species 96
correction 105 first gas-phase species 96
pre-exponential 72, 99, 103 last gas-phase species 96
sticking coefficient 74 surface species 96
Fluent 9 input
FORD 52, 54, 68, 69, 71, 72, 74, 81, 82, 101 gas-phase kinetics 41, 45, 46, 55, 63, 76, 81
formalism surface kinetics 57, 58, 62, 64, 75, 99
atomic site 94, 95 thermodynamic property data 39
mathematical 91 transport property data 76
open site 94, 95 installation
format free 64 manual 11
forward rate constants 99 Installation and Licensing Manual 11
fractions installing 13
mass 96 irreversible reactions 65, 74
mole 92, 93, 97
site 92, 93, 96, 97, 103, 104

K LANG 69, 70, 72, 75

Langmuir-Hinshelwood reactions 69, 72, 106
keywords
auxiliary Latin equation symbols 111
gas-phase reactions Lennard-Jones
collision diameter 76
UNITS 52
potential well depth 76
auxiliary data
LHDE 70, 72
gas-phase reactions 55
LHNU 70, 72
CHEB 51 LHPR 70, 72
DUP 52 Li et al. 34
FORD 52 licensing 13
HIGH 50 manual 11
LOW 50 Lindemann formulation of pressure-dependent reaction 50
lines, blank 59
LT 51 LOW 50, 57
MWOFF 64 LT 51, 57
MWON 64
PCHEB 51
PLOG 51
M
manual
REV 52 installation and licensing 11
RLT 51 mass
RORD 52 density 61
SRI 50 density, gas-phase 97
TCHEB 51 fractions 96
TROE 50 mass-action kinetics 91, 96, 101
surface reactions rate constants 105
material declaration 58
COV 68, 71, 102 mathematical formalism 91
DUP 68, 71, 74 mechanisms See chemistry mechanisms.
FORD 68, 71, 74, 101 messages, diagnostic 73
LANG 72 methane
LHDE 72 chemistry mechanism 33
LHNU 72 microscopic reversibility 102, 106
midpoint temperature 62
LHPR 72 mixture
MWOFF 66, 68, 72 bulk 92, 93
MWON 66, 68, 72 modification of rate expression, surface-coverage 102, 104
NONCON 74 molar concentrations
REV 67, 71, 99 gas species 96
RORD 68, 71, 74, 101 surface site species 97
mole
STICK 65, 67, 68, 71 fractions 93, 97
UNITS 69, 71, 74 mole fractions 92
kinetics data 33 molecular weight 97, 105
kinetics, mass-action 91, 96, 101 Motz-Wise correction 64, 66, 68, 72
MWOFF 64, 66, 68, 72, 75
L MWON 63, 66, 68, 72
Landau Teller 55
Landau-Teller N
reactions 51 names
Landau-Teller rate expressions 90 bulk 61
Landau-Teller reaction 51 site 60

species 60, 61 chemistry mechanisms 33

net production rate 98 methane combustion mechanism 34
next line, continuation 66 Propane-NOx_highT 34
nomenclature 111 properties
NONCON 74 thermodynamic 62, 91, 100
non-integer propyl radical
stoichiometric coefficients 98, 100 methane combustion mechanism 34
non-integer stoichiometric coefficients 98
non-Maxwellian velocity distribution 105
Q
quick reference 79
O
occupancy
number 59 R
site 59 Raoult’s law 92
open site 92, 94 rate
formalism 94, 95 constants 105
order forward 99
reaction 52, 68, 71, 81, 101, 102, 105 mass-action kinetics 105
reverse 99
units 99
P expressions
parameters Arrhenius 64, 65, 107
Arrhenius rate 62, 63, 64, 65, 66, 67, 68, 71, 72, 74, 107 Chebyshev polynomial 51, 88, 89
coverage 68, 71, 102, 103 Eley-Rideal 106
reaction order 52, 68 Landau-Teller 51
reverse rate 52, 71 Langmuir-Hinshelwood 106
PCHEB 51, 57 reverse 52
phase 92, 96 surface-coverage modification of 102
bulk 58, 60, 92, 96 net production 98
density of sites 97 production 98
gas 96 rate of production, species 98
indices 96 user-defined function 46, 64
names 61 rate of progress
surface 58, 98, 100, 105 user-defined function 70
PLOG 51 rate of progress, reaction 68, 96, 100
polarizabilities 76 calculated 106
polynomial rate expressions user-defined function 53, 70
Chebyshev 88, 89 variables 98, 101
potential, chemical 92, 93 rate of progress, reactions 103
pre-exponential factor 72, 99, 103 reactants 65, 67, 94, 99
sticking coefficient 74 reaction
unit conversion 72 adsorption 93, 95
pre-processor, CHEMKIN-CFD 52, 56, 60 chemical 63, 93
gas-phase kinetics 63, 74, 100 chemically activated bimolecular 86
surface kinetics 57, 62, 68, 69, 72, 73, 75, 94, 99, 100 data 64
pressure 92 criteria 65
reactions that depend on 49, 83 error checks 56, 74
units 100 examples of 48, 66
probability 103 summary of the rules 49, 66
problems having no reactions 55 duplicate 52, 67
production rate, species 98 elementary 9, 91, 100, 101
products 65, 67, 94, 99 Eley-Rideal 106
propane global 98

irreversible 65, 74 of phase, density 97

Landau-Teller 51 open 92, 94
Langmuir-Hinshelwood 106 species
order 52, 68, 71, 81, 101, 102, 105 activity 93
parameters type 91, 92, 93
pressure dependence 49 SKUPROD 64, 70
pressure-dependent 83 solution
rate constants, surface 103 ideal 97
rate of progress 68, 96, 100, 103 spaces, blank 64, 66, 71
user-defined function 53 species
reversible 65, 67, 71, 99 bulk 58, 60, 73, 92, 93, 96, 97
sticking-coefficient 63, 66, 68, 74 condensed-phase 60
surface 58, 60, 61, 91, 94, 97, 99, 103 data 77
symbolic description 64 error checks 56
three-body 82 summary of the rules 44
unimolecular/recombination fall-off 83 gas-phase 58, 60, 61, 63, 67, 74, 93, 96, 100, 105
units 52 indices 96
REACTION line 46, 47, 53 names 60, 61
REACTIONS line 64, 70 site 73
real numbers as stoichiometric coefficients 100 surface 93
results, unphysical 102 symbols 65
REV 51, 52, 54, 57, 67, 71, 72, 74, 99 types
reverse rate bulk 91
constants 99 gas-phase 91
parameters 52, 67, 71 surface 91
reversibility, microscopic 102, 106 species rate of production
reversible reaction 52 user-defined function 46
reversible reactions 65, 67, 71, 99 SPECIES section of gas-phase chemistry file 44
RLT 51, 57 SRI 50, 57
RORD 52, 68, 71, 72, 74, 81, 82, 101 standard state
rotational relaxation collision number 77 bulk phase 92
rules site density 58, 60
for auxiliary data, gas-phase reactions 55 STICK 65, 66, 67, 68, 71, 72, 75
for auxiliary data, surface reactions 71 sticking coefficients 63, 64, 65, 66, 67, 68, 72, 74, 103, 105
for bulk data, summary 61 sticking-coefficient
for element data, summary 43 specification 104
for reaction data, summary 49, 66 stoichiometric coefficients 66, 68, 71, 73, 74, 98, 101, 105
for site data, summary 60 non-integer 98, 100
for species data, summary 44 subroutine
for thermodynamic property data, summary 39 user-defined reaction rate of progress 70
subscript equation symbols 118
summary of the rules
S auxiliary data, gas-phase reactions 55
site auxiliary data, surface reactions 71
balance 94 bulk data 61
conservation 91 element data 43
data 58, 63 reaction data 49, 66
error checks 73 site data 60
examples 59 species data 44
summary of the rules for 60 thermodynamic property data 39
densities, surface 58, 100 surface
fractions 92, 93, 96, 97, 103, 104 layer 91
names 60 molar concentration 97
occupancy 59 phase 58, 98, 100, 105

reaction mechanism 63 energy 63, 69, 71

reaction rate constant 103 pressure 100
reactions 58, 60, 61, 91, 94, 97, 99, 103 rate constants 99
site universal gas constant 105
concentration 105 unphysical results 102
density 100 user-defined function 70
species 93 CKUPROG 53
indices 96 reaction rate of progress 53
surface kinetics SKUPROG 70
input 57, 58, 62, 64, 75, 99 species rate of production 46
pre-processor 57, 67, 69, 72, 73, 94, 99, 100 USRPROD keyword 46, 53, 64, 70
surface reaction data USRPROG keyword 53, 70
surface-coverage modification of rate expression 102, 104 USRPROD 46, 64
symbolic description of the reaction 64 USRPROG 53, 70
symbols
chemical 98
species 65 V
variables
reaction rate of progress 98, 101
T velocity
TCHEB 51, 57 distribution, non-Maxwellian 105
temperature
dependence, Arrhenius 99
exponent 72, 99 W
midpoint 63 weight, molecular 97, 105
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
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


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CHEMKIN-CFD for FLUENT Manual

CHEMKIN-CFD for FLUENT Module®

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

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

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

CFD-FLU-20091-0905-UG-1 3 May 2009

A.3.4 Thermodynamic Data.................................................................................................................62

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

© 2009 Reaction Design 4 CFD-FLU-20091-0905-UG-1

2-2 Summary of Advanced CHEMKIN-CFD Parameters .......................................................................................................21

2-3 Diagnostic Output Files Created During a CHEMKIN-CFD Run ......................................................................................26

2-5 Other (non-License) Error Messages in KINetics-log.txt ...............................................................................................31

A-1 Summary of the Rules for Thermodynamic Data ..........................................................................................................39

A-2 Summary of the Rules for Element Data .......................................................................................................................43

A-3 Summary of the Rules for Species Data .......................................................................................................................44

A-4 Reaction Data Criteria ...................................................................................................................................................47

A-5 Summary of the Rules for Gas-phase Reaction Data ...................................................................................................49

A-7 Error Checks .................................................................................................................................................................56

A-8 Summary of the Rules for Site Data ..............................................................................................................................60

A-9 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 Latin Symbols ..............................................................................................................................................................111

C-2 Greek Symbols ............................................................................................................................................................116

CFD-FLU-20091-0905-UG-1 5 May 2009

C-3 Subscript Symbols.......................................................................................................................................................118

© 2009 Reaction Design 6 CFD-FLU-20091-0905-UG-1

2-2 FLUENT Species Model Panel......................................................................................................................................15

2-3 FLUENT Import Chemkin Panel ....................................................................................................................................15

A-2 Equivalent Ways to Describe Element Information .......................................................................................................43

A-3 Equivalent Ways to Describe Species Information........................................................................................................44

A-4 Examples of Reaction Data. ..........................................................................................................................................48

A-5 Examples of Gas-phase Auxiliary Information Data ......................................................................................................54

A-6 Examples of Site Data ...................................................................................................................................................59

A-7 Examples of Bulk Data ..................................................................................................................................................62

A-8 Examples of Surface Reaction Data .............................................................................................................................66

A-9 Examples of Auxiliary Surface Reaction Data ...............................................................................................................72

A-10 Surface Kinetics Input File using Multiple Materials ......................................................................................................75

B-6 Examples of reactions with such non-integer coefficients ...........................................................................................100

B-7 Example of Sticking-coefficient Reaction with No Surface Species ............................................................................104

CFD-FLU-20091-0905-UG-1 7 May 2009

B-8 Example of Sticking-coefficient Reaction with a Surface Site .....................................................................................104

B-9 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

© 2009 Reaction Design 8 CFD-FLU-20091-0905-UG-1

The CHEMKIN-CFD for FLUENT Module incorporates CHEMKIN technology for

CFD-FLU-20091-0905-UG-1 9 May 2009

CHEMKIN-CFD for FLUENT Module

• Dynamic or transient simulation of heat and mass transfer with chemical

1.1 Information Resources

1.1.1 Contents of this Manual

© 2009 Reaction Design 10 CFD-FLU-20091-0905-UG-1

Chapter 2 provides step-by-step procedures for running a CHEMKIN-CFD for FLUENT

1.1.2 Installation and Licensing Manual

CFD-FLU-20091-0905-UG-1 11 © 2009 Reaction Design

© 2009 Reaction Design 12 CFD-FLU-20091-0905-UG-1