Modeling Species Transport and Finite-Rate Chemistry

Chapter 14.
Modeling Species Transport and Finite-Rate

Chemistry
FLUENT can model the mixing and transport of chemical species by solving conserva-
tion equations describing convection, diusion, and reaction sources for each component
species. Multiple simultaneous chemical reactions can be modeled, with reactions occur-
ring in the bulk phase (volumetric reactions) and/or on wall or particle surfaces, and in
the porous region. Species transport modeling capabilities, both with and without reac-
tions, and the inputs you provide when using the model are described in this chapter.
Note that you may also want to consider modeling your turbulent reacting ame using
the mixture fraction approach (for non-premixed systems, described in Chapter 15: Mod-
eling Non-Premixed Combustion), the reaction progress variable approach (for premixed
systems, described in Chapter 16: Modeling Premixed Combustion), the partially pre-
mixed approach (described in Chapter 17: Modeling Partially Premixed Combustion), or
the composition PDF Transport approach (described in Chapter 18: Modeling a Compo-
sition PDF Transport Problem). Modeling multiphase species transport and nite-rate
chemistry can be found in Chapter 23: Modeling Multiphase Flows.
Information is divided into the following sections:
Section 14.1: Volumetric Reactions
Section 14.2: Wall Surface Reactions and Chemical Vapor Deposition
Section 14.3: Particle Surface Reactions
Section 14.4: Species Transport Without Reactions
c Fluent Inc. September 29, 2006 14-1
Modeling Species Transport and Finite-Rate Chemistry
14.1 Volumetric Reactions
Information about species transport and nite-rate chemistry as related to volumetric
reactions is presented in the following subsections:
Section 14.1.1: Theory
Section 14.1.2: Overview of User Inputs for Modeling Species Transport and Reactions
Section 14.1.3: Enabling Species Transport and Reactions and Choosing the Mix-
ture Material
Section 14.1.4: Dening Properties for the Mixture and Its Constituent Species
Section 14.1.5: Dening Boundary Conditions for Species
Section 14.1.6: Dening Other Sources of Chemical Species
Section 14.1.7: Solution Procedures for Chemical Mixing and Finite-Rate Chemistry
Section 14.1.8: Postprocessing for Species Calculations
Section 14.1.9: Importing a Volumetric Kinetic Mechanism in CHEMKIN Format
14-2 c Fluent Inc. September 29, 2006
14.1.1 Theory
Species Transport Equations
When you choose to solve conservation equations for chemical species, FLUENT predicts
the local mass fraction of each species, Y
i
, through the solution of a convection-diusion
equation for the ith species. This conservation equation takes the following general form:
t
(Y
i
) + (vY
i
) =

J
i
+ R
i
+ S
i
(14.1-1)
where R
i
is the net rate of production of species i by chemical reaction (described later
in this section) and S
i
is the rate of creation by addition from the dispersed phase plus
any user-dened sources. An equation of this form will be solved for N 1 species where
N is the total number of uid phase chemical species present in the system. Since the
mass fraction of the species must sum to unity, the Nth mass fraction is determined as
one minus the sum of the N 1 solved mass fractions. To minimize numerical error,
the Nth species should be selected as that species with the overall largest mass fraction,
such as N
2
when the oxidizer is air.
Mass Diffusion in Laminar Flows
In Equation 14.1-1,

J
i
is the diusion ux of species i, which arises due to concentration
gradients. By default, FLUENT uses the dilute approximation, under which the diusion
ux can be written as
J
i
= D
i,m
Y
i
(14.1-2)
Here D
i,m
is the diusion coecient for species i in the mixture.
For certain laminar ows, the dilute approximation may not be acceptable, and full
multicomponent diusion is required. In such cases, the Maxwell-Stefan equations can
be solved; see Section 8.9.2: Full Multicomponent Diusion for details.
Mass Diffusion in Turbulent Flows
In turbulent ows, FLUENT computes the mass diusion in the following form:
J
i
=
_
D
i,m
+

t
Sc
t
_
Y
i
(14.1-3)
where Sc
t
is the turbulent Schmidt number (
t
Dt
where
t
is the turbulent viscosity
and D
t
is the turbulent diusivity). The default Sc
t
is 0.7. Note that turbulent diusion
generally overwhelms laminar diusion, and the specication of detailed laminar diusion
properties in turbulent ows is generally not warranted.
Treatment of Species Transport in the Energy Equation
For many multicomponent mixing ows, the transport of enthalpy due to species diusion
_
n
i=1
h
i
J
i
_
can have a signicant eect on the enthalpy eld and should not be neglected. In par-
ticular, when the Lewis number
Le
i
=
k
c
p
D
i,m
(14.1-4)
for any species is far from unity, neglecting this term can lead to signicant errors. FLU-
ENT will include this term by default. In Equation 14.1-4, k is the thermal conductivity.
Diffusion at Inlets
For the pressure-based solver in FLUENT, the net transport of species at inlets consists
of both convection and diusion components. (For the density-based solvers, only the
convection component is included.) The convection component is xed by the inlet
species mass fraction specied by you. The diusion component, however, depends on
the gradient of the computed species eld at the inlet. Thus the diusion component (and
therefore the net inlet transport) is not specied a priori. See Section 14.1.5: Dening
Boundary Conditions for Species for information about specifying the net inlet transport
of species.
The Generalized Finite-Rate Formulation for Reaction Modeling
The reaction rates that appear as source terms in Equation 14.1-1 are computed in
FLUENT by one of three models:
Laminar nite-rate model: The eect of turbulent uctuations are ignored, and
reaction rates are determined by Arrhenius expressions.
Eddy-dissipation model: Reaction rates are assumed to be controlled by the tur-
bulence, so expensive Arrhenius chemical kinetic calculations can be avoided. The
model is computationally cheap, but, for realistic results, only one or two step
heat-release mechanisms should be used.
Eddy-dissipation-concept (EDC) model: Detailed Arrhenius chemical kinetics can
be incorporated in turbulent ames. Note that detailed chemical kinetic calcula-
tions are computationally expensive.
The generalized nite-rate formulation is suitable for a wide range of applications in-
cluding laminar or turbulent reaction systems, and combustion systems with premixed,
non-premixed, or partially-premixed ames.
The Laminar Finite-Rate Model
The laminar nite-rate model computes the chemical source terms using Arrhenius ex-
pressions, and ignores the eects of turbulent uctuations. The model is exact for laminar
ames, but is generally inaccurate for turbulent ames due to highly non-linear Arrhenius
chemical kinetics. The laminar model may, however, be acceptable for combustion with
relatively slow chemistry and small turbulent uctuations, such as supersonic ames.
The net source of chemical species i due to reaction is computed as the sum of the
Arrhenius reaction sources over the N
R
reactions that the species participate in:
R
i
= M
w,i
N
R
r=1
R
i,r
(14.1-5)
where M
w,i
is the molecular weight of species i and

R
i,r
is the Arrhenius molar rate of
creation/destruction of species i in reaction r. Reaction may occur in the continuous
phase between continuous-phase species only, or at wall surfaces resulting in the surface
deposition or evolution of a continuous-phase species.
Consider the rth reaction written in general form as follows:
N
i=1
i,r
M
i
k
f,r
k
b,r
N
i=1
i,r
M
i
(14.1-6)
where
N = number of chemical species in the system
i,r
= stoichiometric coecient for reactant i in reaction r
i,r
= stoichiometric coecient for product i in reaction r
M
i
= symbol denoting species i
k
f,r
= forward rate constant for reaction r
k
b,r
= backward rate constant for reaction r
Equation 14.1-6 is valid for both reversible and non-reversible reactions. (Reactions in
FLUENT are non-reversible by default.) For non-reversible reactions, the backward rate
constant, k
b,r
, is simply omitted.
The summations in Equation 14.1-6 are for all chemical species in the system, but only
species that appear as reactants or products will have non-zero stoichiometric coecients.
Hence, species that are not involved will drop out of the equation.
For a non-reversible reaction (that is, the Include Backward Reaction button is disabled),
the molar rate of creation/destruction of species i in reaction r (

R
i,r
in Equation 14.1-5)
is given by
R
i,r
=
_
i,r
i,r
_
_
_
k
f,r
N
j=1
[C
j,r
]
(
j,r
+
j,r
)
_
_
(14.1-7)
where
C
j,r
= molar concentration of species j in reaction r (kgmol/m
3
)
j,r
= rate exponent for reactant species j in reaction r
j,r
= rate exponent for product species j in reaction r
For a reversible reaction, the molar rate of creation/destruction of species i in reaction r
is given by
R
i,r
=
_
i,r
i,r
_
_
_
k
f,r
N
j=1
[C
j,r
]
j,r
k
b,r
N
j=1
[C
j,r
]
j,r
_
_
(14.1-8)
Note that the rate exponent for the reverse reaction part in Equation 14.1-8 is always
the product species stoichiometric coecient (
j,r
).
See Section 14.1.4: Inputs for Reaction Denition for information about inputting the
stoichiometric coecients and rate exponents for both global forward (non-reversible)
reactions and elementary (reversible) reactions.
represents the net eect of third bodies on the reaction rate. This term is given by
=
N
j,r
C
j
(14.1-9)
where
j,r
is the third-body eciency of the jth species in the rth reaction. By default,
FLUENT does not include third-body eects in the reaction rate calculation. You can,
however, opt to include the eect of third-body eciencies if you have data for them.
The forward rate constant for reaction r, k
f,r
, is computed using the Arrhenius expression
k
f,r
= A
r
T
r
e
Er/RT
(14.1-10)
where
A
r
= pre-exponential factor (consistent units)
r
= temperature exponent (dimensionless)
E
r
= activation energy for the reaction (J/kgmol)
R = universal gas constant (J/kgmol-K)
You (or the database) will provide values for
i,r
,
i,r
,
j,r
,
j,r
,
r
, A
r
, E
r
, and, optionally,
j,r
during the problem denition in FLUENT.
If the reaction is reversible, the backward rate constant for reaction r, k
b,r
, is computed
from the forward rate constant using the following relation:
k
b,r
=
k
f,r
K
r
(14.1-11)
where K
r
is the equilibrium constant for the rth reaction, computed from
K
r
= exp
_
S
0
r
R

H
0
r
RT
_
_
p
atm
RT
_
N
i=1
(
i,r
i,r
)
(14.1-12)
where p
atm
denotes atmospheric pressure (101325 Pa). The term within the exponential
function represents the change in Gibbs free energy, and its components are computed
as follows:
S
0
r
R
=
N
i=1
_
i,r
i,r
_
S
0
i
R
(14.1-13)
H
0
r
RT
=
N
i=1
_
i,r
i,r
_
h
0
i
RT
(14.1-14)
where S
0
i
and h
0
i
are the standard-state entropy and standard-state enthalpy (heat of
formation). These values are specied in FLUENT as properties of the mixture material.
Pressure-Dependent Reactions
FLUENT can use one of three methods to represent the rate expression in pressure-
dependent (or pressure fall-o) reactions. A fall-o reaction is one in which the tem-
perature and pressure are such that the reaction occurs between Arrhenius high-pressure
and low-pressure limits, and thus is no longer solely dependent on temperature.
There are three methods of representing the rate expressions in this fall-o region. The
simplest one is the Lindemann [211] form. There are also two other related methods, the
Troe method [120] and the SRI method [356], that provide a more accurate description
of the fall-o region.
Arrhenius rate parameters are required for both the high- and low-pressure limits. The
rate coecients for these two limits are then blended to produce a smooth pressure-
dependent rate expression. In Arrhenius form, the parameters for the high-pressure limit
(k) and the low-pressure limit (k
low
) are as follows:
k = AT
e
E/RT
(14.1-15)
k
low
= A
low
T
low
e
E
low
/RT
(14.1-16)
The net rate constant at any pressure is then taken to be
k
net
= k
_
p
r
1 + p
r
_
F (14.1-17)
where p
r
is dened as
p
r
=
k
low
[M]
k
(14.1-18)
and [M] is the concentration of the bath gas, which can include third-body eciencies.
If the function F in Equation 14.1-17 is unity, then this is the Lindemann form. FLUENT
provides two other forms to describe F, namely the Troe method and the SRI method.
In the Troe method, F is given by
log F =
_
_
_
1 +
_
log p
r
+ c
n d(log p
r
+ c)
_
2
_
_
_
1
log F
cent
(14.1-19)
where
c = 0.4 0.67 log F
cent
(14.1-20)
n = 0.75 1.27 log F
cent
(14.1-21)
d = 0.14 (14.1-22)
and
F
cent
= (1 )e
T/T
3
+ e
T/T
1
+ e
T
2
/T
(14.1-23)
The parameters , T
3
, T
2
, and T
1
are specied as inputs.
In the SRI method, the blending function F is approximated as
F = d
_
a exp
_
b
T
_
+ exp
_
T
c
_
_
X
T
e
(14.1-24)
where
X =
1
1 + log
2
p
r
(14.1-25)
In addition to the three Arrhenius parameters for the low-pressure limit (k
low
) expression,
you must also supply the parameters a, b, c, d, and e in the F expression.
i
Chemical kinetic mechanisms are usually highly non-linear and form a
set of sti coupled equations. See Section 14.1.7: Solution Procedures
for Chemical Mixing and Finite-Rate Chemistry for solution procedure
guidelines. Also, if you have a chemical mechanism in CHEMKIN [177]
format, you can import this mechanism into FLUENT as described in
Section 14.1.9: Importing a Volumetric Kinetic Mechanism in CHEMKIN
Format.
The Eddy-Dissipation Model
Most fuels are fast burning, and the overall rate of reaction is controlled by turbulent
mixing. In non-premixed ames, turbulence slowly convects/mixes fuel and oxidizer into
the reaction zones where they burn quickly. In premixed ames, the turbulence slowly
convects/mixes cold reactants and hot products into the reaction zones, where reaction
occurs rapidly. In such cases, the combustion is said to be mixing-limited, and the
complex, and often unknown, chemical kinetic rates can be safely neglected.
FLUENT provides a turbulence-chemistry interaction model, based on the work of Mag-
nussen and Hjertager [228], called the eddy-dissipation model. The net rate of production
of species i due to reaction r, R
i,r
, is given by the smaller (i.e., limiting value) of the two
expressions below:
R
i,r
=
i,r
M
w,i
A
k
min
R
_
Y
R
R,r
M
w,R
_
(14.1-26)
R
i,r
=
i,r
M
w,i
AB
P
Y
P
N
j

j,r
M
w,j
(14.1-27)
where Y
P
is the mass fraction of any product species, P
Y
R
is the mass fraction of a particular reactant, R
A is an empirical constant equal to 4.0
B is an empirical constant equal to 0.5
In Equations 14.1-26 and 14.1-27, the chemical reaction rate is governed by the large-
eddy mixing time scale, k/, as in the eddy-breakup model of Spalding [349]. Combustion
proceeds whenever turbulence is present (k/ > 0), and an ignition source is not required
to initiate combustion. This is usually acceptable for non-premixed ames, but in pre-
mixed ames, the reactants will burn as soon as they enter the computational domain,
upstream of the ame stabilizer. To remedy this, FLUENT provides the nite-rate/eddy-
dissipation model, where both the Arrhenius (Equation 14.1-8), and eddy-dissipation
(Equations 14.1-26 and 14.1-27) reaction rates are calculated. The net reaction rate is
taken as the minimum of these two rates. In practice, the Arrhenius rate acts as a ki-
netic switch, preventing reaction before the ame holder. Once the ame is ignited,
the eddy-dissipation rate is generally smaller than the Arrhenius rate, and reactions are
mixing-limited.
i
Although FLUENT allows multi-step reaction mechanisms (number of reac-
tions > 2) with the eddy-dissipation and nite-rate/eddy-dissipation mod-
els, these will likely produce incorrect solutions. The reason is that multi-
step chemical mechanisms are based on Arrhenius rates, which dier for
each reaction. In the eddy-dissipation model, every reaction has the same,
turbulent rate, and therefore the model should be used only for one-step
(reactant product), or two-step (reactant intermediate, intermediate
product) global reactions. The model cannot predict kinetically con-
trolled species such as radicals. To incorporate multi-step chemical kinetic
mechanisms in turbulent ows, use the EDC model (described below).
i
The eddy-dissipation model requires products to initiate reaction (see
Equation 14.1-27). When you initialize the solution for steady ows, FLU-
ENT sets all species mass fractions to a maximum of the user specied ini-
tial value and 0.01. This is usually sucient to start the reaction. However,
if you converge a mixing solution rst, where all product mass fractions
are zero, you may then have to patch products into the reaction zone to
ignite the ame. See Section 14.1.7: Ignition in Combustion Simulations
for details.
The Eddy-Dissipation Model for LES
When the LES turbulence model is used, the turbulent mixing rate, /k in Equa-
tions 14.1-26 and 14.1-27, is replaced by the subgrid-scale mixing rate. This is calculated
as
1
sgs
=
_
2S
ij
S
ij
(14.1-28)
where
1
sgs
= subgrid-scale mixing rate (s
1
)
S
ij
=
1
2
_
u
i
x
j
+
u
j
x
i
_
= strain rate tensor (s
1
)
The Eddy-Dissipation-Concept (EDC) Model
The eddy-dissipation-concept (EDC) model is an extension of the eddy-dissipation model
to include detailed chemical mechanisms in turbulent ows [227]. It assumes that reaction
occurs in small turbulent structures, called the ne scales. The length fraction of the ne
scales is modeled as [125]
= C
k
2
_
1/4
(14.1-29)
where

denotes ne-scale quantities and
C
= volume fraction constant = 2.1377

= kinematic viscosity
The volume fraction of the ne scales is calculated as
3
. Species are assumed to react
in the ne structures over a time scale
= C
_
1/2
(14.1-30)
where C
is a time scale constant equal to 0.4082.

In FLUENT, combustion at the ne scales is assumed to occur as a constant pressure reac-
tor, with initial conditions taken as the current species and temperature in the cell. Reac-
tions proceed over the time scale
, governed by the Arrhenius rates of Equation 14.1-8,

and are integrated numerically using the ISAT algorithm [289]. ISAT can accelerate the
chemistry calculations by two to three orders of magnitude, oering substantial reduc-
tions in run-times. Details about the ISAT algorithm may be found in Sections 18.2.4
and 18.2.5. ISAT is very powerful, but requires some care. See Section 18.3.9: Using
ISAT Eciently for details on using ISAT eciently.
The source term in the conservation equation for the mean species i, Equation 14.1-1, is
modeled as
R
i
=
(
)
2
[1 (
)
3
]
(Y
i
Y
i
) (14.1-31)
where Y
i
is the ne-scale species mass fraction after reacting over the time
.
The EDC model can incorporate detailed chemical mechanisms into turbulent reacting
ows. However, typical mechanisms are invariably sti and their numerical integration
is computationally costly. Hence, the model should be used only when the assumption
of fast chemistry is invalid, such as modeling the slow CO burnout in rapidly quenched
ames, or the NO conversion in selective non-catalytic reduction (SNCR).
See Section 14.1.7: Solution of Sti Laminar Chemistry Systems for guidelines on obtain-
ing a solution using the EDC model.
14.1.2 Overview of User Inputs for Modeling Species Transport and Reactions
The basic steps for setting up a problem involving species transport and reactions are
listed below, and the details about performing each step are presented in Sections 14.1.3
14.1.5. Additional information about setting up and solving the problem is provided in
Sections 14.1.614.1.8.
1. Enable species transport and volumetric reactions, and specify the mixture mate-
rial. See Section 14.1.3: Enabling Species Transport and Reactions and Choosing
the Mixture Material. (The mixture material concept is explained below.)
2. If you are also modeling wall or particle surface reactions, turn on wall surface
and/or particle surface reactions as well. See Sections 14.2 and 14.3 for details.
3. Check and/or dene the properties of the mixture. (See Section 14.1.4: Dening
Properties for the Mixture and Its Constituent Species.) Mixture properties include
the following:
species in the mixture
reactions
other physical properties (e.g., viscosity, specic heat)
4. Check and/or set the properties of the individual species in the mixture. (See
Section 14.1.4: Dening Properties for the Mixture and Its Constituent Species.)
5. Set species boundary conditions. (See Section 14.1.5: Dening Boundary Condi-
tions for Species.)
In many cases, you will not need to modify any physical properties because the solver
gets species properties, reactions, etc. from the materials database when you choose
the mixture material. Some properties, however, may not be dened in the database.
You will be warned when you choose your material if any required properties need to
be set, and you can then assign appropriate values for these properties. You may also
want to check the database values of other properties to be sure that they are correct for
your particular application. For details about modifying an existing mixture material or
creating a new one from scratch, see Section 14.1.4: Dening Properties for the Mixture
and Its Constituent Species. Modications to the mixture material can include the
following:
Addition or removal of species
Changing the chemical reactions
Modifying other material properties for the mixture
Modifying material properties for the mixtures constituent species
If you are solving a reacting ow, you will usually want to dene the mixtures specic
heat as a function of composition, and the specic heat of each species as a function of
temperature. You may want to do the same for other properties as well. By default,
constant properties are used, but for the properties of some species, there is a piecewise-
polynomial function of temperature that exists in the database and is available for your
use. You may also choose to specify a dierent temperature-dependent function if you
know of one that is more suitable for your problem.
Mixture Materials
The concept of mixture materials has been implemented in FLUENT to facilitate the
setup of species transport and reacting ow. A mixture material may be thought of as a
set of species and a list of rules governing their interaction. The mixture material carries
with it the following information:
A list of the constituent species, referred to as uid materials
A list of mixing laws dictating how mixture properties (density, viscosity, specic
heat, etc.) are to be derived from the properties of individual species if composition-
dependent properties are desired
A direct specication of mixture properties if composition-independent properties
are desired
Diusion coecients for individual species in the mixture
Other material properties (e.g., absorption and scattering coecients) that are not
associated with individual species
A set of reactions, including a reaction type (nite-rate, eddy-dissipation, etc.) and
stoichiometry and rate constants
Both mixture materials and uid materials are stored in the FLUENT materials database.
Many common mixture materials are included (e.g., methane-air, propane-air). Gener-
ally, one/two-step reaction mechanisms and many physical properties of the mixture and
its constituent species are dened in the database. When you indicate which mixture
material you want to use, the appropriate mixture material, uid materials, and proper-
ties are loaded into the solver. If any necessary information about the selected material
(or the constituent uid materials) is missing, the solver will inform you that you need to
specify it. In addition, you may choose to modify any of the predened properties. See
Section 8.1.2: Using the Materials Panel for information about the sources of FLUENTs
database property data.
For example, if you plan to model combustion of a methane-air mixture, you do not need
to explicitly specify the species involved in the reaction or the reaction itself. You will
simply select methane-air as the mixture material to be used, and the relevant species
(CH
4
, O
2
, CO
2
, H
2
O, and N
2
) and reaction data will be loaded into the solver from the
database. You can then check the species, reactions, and other properties and dene
any properties that are missing and/or modify any properties for which you wish to
use dierent values or functions. You will generally want to dene a composition- and
temperature-dependent specic heat, and you may want to dene additional properties
as functions of temperature and/or composition.
The use of mixture materials gives you the exibility to use one of the many predened
mixtures, modify one of these mixtures, or create your own mixture material. Cus-
tomization of mixture materials is performed in the Materials panel, as described in
Section 14.1.4: Dening Properties for the Mixture and Its Constituent Species.
14.1.3 Enabling Species Transport and Reactions and Choosing the Mixture
Material
The problem setup for species transport and volumetric reactions begins in the Species
Model panel (Figure 14.1.1). For cases which involve multiphase species transport and
reactions, refer to Section 23.8: Modeling Species Transport in Multiphase Flows.
Dene Models Species Transport & Reaction...
Figure 14.1.1: The Species Model Panel
1. Under Model, select Species Transport.
2. Under Reactions, turn on Volumetric.
3. In the Mixture Material drop-down list under Mixture Properties, choose which mix-
ture material you want to use in your problem. The drop-down list will include
all of the mixtures that are currently dened in the database. To check the prop-
erties of a mixture material, select it and click the Edit... button. If the mixture
you want to use is not in the list, choose the mixture-template material, and see
Section 14.1.4: Dening Properties for the Mixture and Its Constituent Species for
details on setting your mixtures properties. If there is a mixture material listed
that is similar to your desired mixture, you may choose that material and see Sec-
tion 14.1.4: Dening Properties for the Mixture and Its Constituent Species for
details on modifying properties of an existing material.
When you choose the Mixture Material, the Number of Volumetric Species in the
mixture will be displayed in the panel for your information.
i
Note that if you re-open the Species Model panel after species transport
has already been enabled, only the mixture materials available in your case
will appear in the list. You can add more mixture materials to your case
by copying them from the database, as described in Section 8.1.2: Copying
Materials from the FLUENT Database, or by creating a new mixture, as
described in Sections 8.1.2 and 14.1.4.
As mentioned in Section 14.1.2: Mixture Materials, modeling parameters for the
species transport and (if relevant) reactions will automatically be loaded from the
database. If any information is missing, you will be informed of this after you
click on OK in the Species Model panel. If you want to check or modify any prop-
erties of the mixture material, you will use the Materials panel, as described in
Section 14.1.4: Dening Properties for the Mixture and Its Constituent Species.
4. Choose the Turbulence-Chemistry Interaction model. Four models are available:
Laminar Finite-Rate computes only the Arrhenius rate (see Equation 14.1-8) and
neglects turbulence-chemistry interaction.
Finite-Rate/Eddy-Dissipation (for turbulent ows) computes both the Arrhenius
rate and the mixing rate and uses the smaller of the two.
Eddy-Dissipation (for turbulent ows) computes only the mixing rate (see Equa-
tions 14.1-26 and 14.1-27).
EDC (for turbulent ows) models turbulence-chemistry interaction with detailed
chemical mechanisms (see Equations 14.1-8 and 14.1-31).
5. If you selected EDC, you have the option to modify the Volume Fraction Constant
and the Time Scale Constant (C
in Equation 14.1-29 and C
in Equation 14.1-30),
although the default values are recommended. Further, to reduce the computational
expense of the chemistry calculations, you can increase the number of Flow Iterations
per Chemistry Update. By default, FLUENT will update the chemistry one per 10
ow iterations. For details about using the Integration Parameters... option, under
Reactions, see Section 18.3: Steps for Using the Composition PDF Transport Model.
6. (optional) If you want to model full multicomponent diusion or thermal diusion,
turn on the Full Multicomponent Diusion or Thermal Diusion option.
See Section 8.9.2: Full Multicomponent Diusion for details.
7. Enabling KINetics from Reaction Design for laminar reactions, will allow you to use
the proprietary reaction-rate utilities and solution algorithms from Reaction Design,
which is based on and compatible with their CHEMKIN technology [177]. For EDC
Turbulence-Chemistry Interaction and the Composition PDF Transport model, en-
abling the KINetics from Reaction Design option will allow you to use reaction rates
from Reaction Designs KINetics module, instead of the default FLUENT reaction
rates. FLUENTs ISAT algorithm is employed to integrate these rates. Please refer
to the KINetics for Fluent manual [3] from Reaction Design for details on the chem-
istry formulation options. For more information, or to obtain a license to the Flu-
ent/KINetics module, please contact Reaction Design at info@reactiondesign.com
or +1 858-550-1920, or go to http://www.reactiondesign.com
14.1.4 Dening Properties for the Mixture and Its Constituent Species
As discussed in Section 14.1.2: Overview of User Inputs for Modeling Species Transport
and Reactions, if you use a mixture material from the database, most mixture and species
properties will already be dened. You may follow the procedures in this section to check
the current properties, modify some of the properties, or set all properties for a brand-new
mixture material that you are dening from scratch.
Remember that you will need to dene properties for the mixture material and also for its
constituent species. It is important that you dene the mixture properties before setting
any properties for the constituent species, since the species property inputs may depend
on the methods you use to dene the properties of the mixture. The recommended
sequence for property inputs is as follows:
1. Dene the mixture species, and reaction(s), and dene physical properties for the
mixture. Remember to click on the Change/Create button when you are done
setting properties for the mixture material.
2. Dene physical properties for the species in the mixture. Remember to click on the
Change/Create button after dening the properties for each species.
These steps, all of which are performed in the Materials panel, are described in detail in
this section.
Dene Materials...
Dening the Species in the Mixture
If you are using a mixture material from the database, the species in the mixture will
already be dened for you. If you are creating your own material or modifying the species
in an existing material, you will need to dene them yourself.
In the Materials panel (Figure 14.1.2), check that the Material Type is set to mixture and
your mixture is selected in the Fluent Mixture Materials list. Click on the Edit... button
to the right of Mixture Species to open the Species panel (Figure 14.1.3).
Figure 14.1.2: The Materials Panel (showing a mixture material)
Figure 14.1.3: The Species Panel
Overview of the Species Panel
In the Species panel, the Selected Species list shows all of the uid-phase species in the
mixture. If you are modeling wall or particle surface reactions, the Selected Solid Species
list will show all of the bulk solid species in the mixture. Solid species are species that
are created or evolved from wall boundaries or discrete-phase particles (e.g., Si(s)) and
do not exist as uid-phase species.
If you are modeling wall surface reactions, the Selected Site Species list will show all of the
site species in the mixture. Site species are species that are adsorbed to a wall boundary.
The use of solid and site species with wall surface reactions is described in Section 14.2: Wall
Surface Reactions and Chemical Vapor Deposition. See Section 14.3: Particle Surface
Reactions for information about particle surface reactions.
i
The order of the species in the Selected Species list is very important.
FLUENT considers the last species in the list to be the bulk species. You
should therefore be careful to retain the most abundant species (by mass)
as the last species when you add species to or delete species from a mixture
material.
The Available Materials list shows materials that are available but not in the mixture.
Generally you will see air in this list, since air is always available by default.
Adding Species to the Mixture
If you are creating a mixture from scratch or starting from an existing mixture and adding
some missing species, you will rst need to load the desired species from the database
(or create them, if they are not present in the database) so that they will be available to
the solver. The procedure for adding species is listed below. (You will need to close the
Species panel before you begin, since it is a modal panel that will not allow you to do
anything else when it is open.)
1. In the Materials panel, click on the Fluent Database... button to open the Flu-
ent Database Materials panel and copy the desired species, as described in Sec-
tion 8.1.2: Copying Materials from the FLUENT Database. Remember that the
constituent species of the mixture are uid materials, so you should select uid as
the Material Type in the Fluent Database Materials panel to see the correct list of
choices. Note that available solid species (for surface reactions) are also contained
in the uid list.
i
If you do not see the species you are looking for in the database, you can
create a new uid material for that species, following the instructions in
Section 8.1.2: Creating a New Material, and then continue with step 2,
below.
2. Re-open the Species panel, as described above. You will see that the uid materials
you copied from the database (or created) are listed in the Available Materials list.
3. To add a species to the mixture, select it in the Available Materials list and click on
the Add button below the Selected Species list (or below the Selected Site Species
or Selected Solid Species list, to dene a site or solid species). The species will be
added to the end of the relevant list and removed from the Available Materials list.
4. Repeat the previous step for all the desired species. When you are nished, click
on the OK button.
i
Adding a species to the list will alter the order of the species. You should
be sure that the last species in the list is the bulk species, and you should
check any boundary conditions, under-relaxation factors, or other solution
parameters that you have set, as described in detail below.
Removing Species from the Mixture
To remove a species from the mixture, simply select it in the Selected Species list (or the
Selected Site Species or Selected Solid Species list) and click on the Remove button below
the list. The species will be removed from the list and added to the Available Materials
list.
i
Removing a species from the list will alter the order of the species. You
should be sure that the last species in the list is the bulk species, and you
should check any boundary conditions, under-relaxation factors, or other
solution parameters that you have set, as described in detail below.
Reordering Species
If you nd that the last species in the Selected Species list is not the most abundant
species (as it must be), you will need to rearrange the species to obtain the proper order.
1. Remove the bulk species from the Selected Species list. It will now appear in the
Available Species list.
2. Add the species back in again. It will automatically be placed at the end of the
list.
The Naming and Ordering of Species
As discussed above, you must retain the most abundant species as the last one in the
Selected Species list when you add or remove species. Additional considerations you
should be aware of when adding and deleting species are presented here.
There are three characteristics of a species that identify it to the solver: name, chem-
ical formula, and position in the list of species in the Species panel. Changing these
characteristics will have the following eects:
You can change the Name of a species (using the Materials panel, as described in
Section 8.1.2: Renaming an Existing Material) without any consequences.
You should never change the given Chemical Formula of a species.
You will change the order of the species list if you add or remove any species.
When this occurs, all boundary conditions, solver parameters, and solution data
for species will be reset to the default values. (Solution data, boundary conditions,
and solver parameters for other ow variables will not be aected.) Thus, if you
add or remove species you should take care to redene species boundary conditions
and solution parameters for the newly dened problem. In addition, you should
recognize that patched species concentrations or concentrations stored in any data
le that was based on the original species ordering will be incompatible with the
newly dened problem. You can use the data le as a starting guess, but you should
be aware that the species concentrations in the data le may provide a poor initial
guess for the newly dened model.
Dening Reactions
If your FLUENT model involves chemical reactions, you can next dene the reactions in
which the dened species participate. This will be necessary only if you are creating a
mixture material from scratch, you have modied the species, or you want to redene
the reactions for some other reason.
Depending on which turbulence-chemistry interaction model you selected in the Species
Model panel (see Section 14.1.3: Enabling Species Transport and Reactions and Choos-
ing the Mixture Material), the appropriate reaction model will be displayed in the Re-
action drop-down list in the Materials panel. If you are using the laminar nite-rate or
EDC model, the reaction model will be nite-rate; if you are using the eddy-dissipation
model, the reaction model will be eddy-dissipation; if you are using the nite-rate/eddy-
dissipation model, the reaction model will be nite-rate/eddy-dissipation.
Inputs for Reaction Denition
To dene the reactions, click on the Edit... button to the right of Reaction. The Reactions
panel (Figure 14.1.4) will open.
The steps for dening reactions are as follows:
1. Set the total number of reactions (volumetric reactions, wall surface reactions, and
particle surface reactions) in the Total Number of Reactions eld. (Use the arrows
to change the value, or type in the value and press RETURN.)
Note that if your model includes discrete-phase combusting particles, you should
include the particulate surface reaction(s) (e.g., char burnout, multiple char ox-
idation) in the number of reactions only if you plan to use the multiple surface
reactions model for surface combustion.
2. Specify the Reaction Name of the reaction you want to dene.
3. Set the ID of the reaction you want to dene. (Again, if you type in the value be
sure to press RETURN.)
4. If this is a uid-phase reaction, keep the default selection of Volumetric as the
Reaction Type. If this is a wall surface reaction (described in Section 14.2: Wall
Surface Reactions and Chemical Vapor Deposition) or a particle surface reaction
(described in Section 14.3: Particle Surface Reactions), select Wall Surface or Particle
Surface as the Reaction Type. See Section 14.3.2: User Inputs for Particle Surface
Reactions for further information about dening particle surface reactions.
Figure 14.1.4: The Reactions Panel
5. Specify how many reactants and products are involved in the reaction by increas-
ing the value of the Number of Reactants and the Number of Products. Select each
reactant or product in the Species drop-down list and then set its stoichiometric co-
ecient and rate exponent in the appropriate Stoich. Coecient and Rate Exponent
elds. (The stoichiometric coecient is the constant
i,r
or
i,r
in Equation 14.1-6
and the rate exponent is the exponent on the reactant or product concentration,
j,r
or
j,r
in Equation 14.1-8.)
There are two general classes of reactions that can be handled by the Reactions
panel, so it is important that the parameters for each reaction are entered correctly.
The classes of reactions are as follows:
Global forward reaction (no reverse reaction): Product species generally do
not aect the forward rate, so the rate exponent for all products (
j,r
) should
be 0. For reactant species, set the rate exponent (
j,r
) to the desired value. If
such a reaction is not an elementary reaction, the rate exponent will generally
not be equal to the stoichiometric coecient (
i,r
) for that species. An example
of a global forward reaction is the combustion of methane:
CH
4
+ 2O
2
CO
2
+ 2H
2
O
where
CH
4
= 1,
CH
4
= 0.2,
O
2
= 2,
O
2
= 1.3,
CO
2
= 1,
CO
2
= 0,
H
2
O
= 2,
and
H
2
O
= 0.
Figure 14.1.4 shows the coecient inputs for the combustion of methane. (See
also the methane-air mixture material in the Database Materials panel.)
Note that, in certain cases, you may wish to model a reaction where product
species aect the forward rate. For such cases, set the product rate exponent
(
j,r
) to the desired value. An example of such a reaction is the gas-shift re-
action (see the carbon-monoxide-air mixture material in the Database Materials
panel), in which the presence of water has an eect on the reaction rate:
CO +
1
2
O
2
+ H
2
O CO
2
+ H
2
O
In the gas-shift reaction, the rate expression may be dened as:
k[CO][O
2
]
1/4
[H
2
O]
1/2
where
CO
= 1,
CO
= 1,
O
2
= 0.5,
O
2
= 0.25,
CO
2
= 1,
CO
2
= 0,
H
2
O
= 0,
and
H
2
O
= 0.5.
Reversible reaction: An elementary chemical reaction that assumes the rate
exponent for each species is equivalent to the stoichiometric coecient for that
species. An example of an elementary reaction is the oxidation of SO
2
to SO
3
:
SO
2
+
1
2
O
2

SO
3
where
SO
2
= 1,
SO
2
= 1,
O
2
= 0.5,
O
2
= 0.5,
SO
3
= 1, and
SO
3
= 1.
See step 6 below for information about how to enable reversible reactions.
6. If you are using the laminar nite-rate, nite-rate/eddy-dissipation, or EDC model
for the turbulence-chemistry interaction, enter the following parameters for the
Arrhenius rate under the Arrhenius Rate heading:
Pre-Exponential Factor (the constant A
r
in Equation 14.1-10). The units of A
r
must be specied such that the units of the molar reaction rate,

R
i,r
in Equa-
tion 14.1-5, are moles/volume-time (e.g., kgmol/m
3
-s) and the units of the
volumetric reaction rate, R
i
in Equation 14.1-5, are mass/volume-time (e.g.,
kg/m
3
-s).
i
It is important to note that if you have selected the British units system,
the Arrhenius factor should still be input in SI units. This is because
FLUENT applies no conversion factor to your input of A
r
(the conversion
factor is 1.0) when you work in British units, as the correct conversion
factor depends on your inputs for
i,r
,
r
, etc.
Activation Energy (the constant E
r
in the forward rate constant expression, Equa-
tion 14.1-10).
Temperature Exponent (the value for the constant
r
in Equation 14.1-10).
Third-Body Eciencies (the values for
j,r
in Equation 14.1-9). If you have ac-
curate data for the eciencies and want to include this eect on the reaction
rate (i.e., include in Equation 14.1-8), turn on the Third Body Eciencies
option and click on the Specify... button to open the Third-Body Eciencies
panel (Figure 14.1.5). For each Species in the panel, specify the Third-Body
Eciencies.
i
It is not necessary to include the third-body eciencies. You should not
enable the Third-Body Eciencies option unless you have accurate data for
these parameters.
Figure 14.1.5: The Third-Body Eciencies Panel
Pressure-Dependent Reaction (if relevant) If you are using the laminar nite-rate
or EDC model for turbulence-chemistry interaction, or have enabled the com-
position PDF transport model (see Chapter 18: Modeling a Composition PDF
Transport Problem), and the reaction is a pressure fall-o reaction (see Sec-
tion 14.1.1: Pressure-Dependent Reactions), turn on the Pressure-Dependent
Reaction option for the Arrhenius Rate and click on the Specify... button to
open the Pressure-Dependent Reaction panel (Figure 14.1.6).
Under Reaction Parameters, select the appropriate Reaction Type (lindemann,
troe, or sri). See Section 14.1.1: Pressure-Dependent Reactions for details
about the three methods. Next, you must specify if the Bath Gas Concentration
([M] in Equation 14.1-18) is to be dened as the concentration of the mixture,
or as the concentration of one of the mixtures constituent species, by selecting
the appropriate item in the drop-down list.
The parameters you specied under Arrhenius Rate in the Reactions panel
represent the high-pressure Arrhenius parameters. You can, however, specify
values for the following parameters under Low Pressure Arrhenius Rate:
ln(Pre-Exponential Factor) (A
low
in Equation 14.1-16) The pre-exponential
factor A
low
is often an extremely large number, so you will input the
natural logarithm of this term.
Activation Energy (E
low
in Equation 14.1-16)
Temperature Exponent (
low
in Equation 14.1-16)
If you selected troe for the Reaction Type, you can specify values for Alpha, T1,
T2, and T3 (, T
1
, T
2
, and T
3
in Equation 14.1-23) under Troe parameters. If
you selected sri for the Reaction Type, you can specify values for a, b, c, d, and
e (a, b, c, d, and e in Equation 14.1-24) under SRI parameters.
Figure 14.1.6: The Pressure-Dependent Reaction Panel
7. If you are using the laminar nite-rate or EDC model for turbulence-chemistry
interaction, and the reaction is reversible, turn on the Include Backward Reaction
option for the Arrhenius Rate. When this option is enabled, you will not be able
to edit the Rate Exponent for the product species, which instead will be set to be
equivalent to the corresponding product Stoich. Coecient. If you do not wish to
use FLUENTs default values, or if you are dening your own reaction, you will also
need to specify the standard-state enthalpy and standard-state entropy, to be used
in the calculation of the backward reaction rate constant (Equation 14.1-11). Note
that the reversible reaction option is not available for either the eddy-dissipation
or the nite-rate/eddy-dissipation turbulence-chemistry interaction model.
8. If you are using the eddy-dissipation or nite-rate/eddy-dissipation model for
turbulence-chemistry interaction, you can enter values for A and B under the Mixing
Rate heading. Note, however, that these values should not be changed unless you
have reliable data. In most cases you will simply use the default values.
A is the constant A in the turbulent mixing rate (Equations 14.1-26 and 14.1-27)
when it is applied to a species that appears as a reactant in this reaction. The
default setting of 4.0 is based on the empirically derived values given by Magnussen
et al. [228].
B is the constant B in the turbulent mixing rate (Equation 14.1-27) when it is
applied to a species that appears as a product in this reaction. The default setting
of 0.5 is based on the empirically derived values given by Magnussen et al. [228].
9. Repeat steps 28 for each reaction you need to dene. When you are nished
dening all reactions, click OK.
Dening Species and Reactions for Fuel Mixtures
Quite often, combustion systems will include fuel that is not easily described as a pure
species (such as CH
4
or C
2
H
6
). Complex hydrocarbons, including fuel oil or even wood
chips, may be dicult to dene in terms of such pure species. However, if you have
available the heating value and the ultimate analysis (elemental composition) of the
fuel, you can dene an equivalent fuel species and an equivalent heat of formation for
this fuel. Consider, for example, a fuel known to contain 50% C, 6% H, and 44% O by
weight. Dividing by atomic weights, you can arrive at a fuel species with the molecular
formula C
4.17
H
6
O
2.75
. You can start from a similar, existing species or create a species
from scratch, and assign it a molecular weight of 100.04 (4.17 12 + 6 1 + 2.75
16). The chemical reaction would be considered to be
C
4.17
H
6
O
2.75
+ 4.295O
2
4.17CO
2
+ 3H
2
O
You will need to set the appropriate stoichiometric coecients for this reaction.
The heat of formation (or standard-state enthalpy) for the fuel species can be calculated
from the known heating value H since
H =
N
i=1
h
0
i
_
i,r
i,r
_
(14.1-32)
where h
0
i
is the standard-state enthalpy on a molar basis. Note the sign convention in
Equation 14.1-32: H is negative when the reaction is exothermic.
Dening Zone-Based Reaction Mechanisms
If your FLUENT model involves reactions that are conned to a specic area of the
domain, you can dene reaction mechanisms to enable dierent reactions selectively in
dierent geometrical zones. You can create reaction mechanisms by selecting reactions
from those dened in the Reactions panel and grouping them. You can then assign a
particular mechanism to a particular zone.
Inputs for Reaction Mechanism Denition
To dene a reaction mechanism, click on the Edit... button to the right of Mechanism.
The Reaction Mechanisms panel (Figure 14.1.7) will open.
Figure 14.1.7: The Reaction Mechanisms Panel
The steps for dening a reaction mechanism are as follows:
1. Set the total number of mechanisms in the Number of Mechanisms eld. (Use the
arrows to change the value, or type the value and press RETURN.)
2. Set the Mechanism ID of the mechanism you want to dene. (Again, if you type in
the value, be sure to press RETURN.)
3. Specify the Name of the mechanism.
4. Select the type of reaction to add to the mechanism under Reaction Type. If you
select Volumetric, the Reactions list will display all available uid-phase reactions. If
you select Wall Surface or Particle Surface, the Reactions list will display all available
wall surface reactions (described in Section 14.2: Wall Surface Reactions and Chem-
ical Vapor Deposition) or particle surface reactions (described in Section 14.3: Par-
ticle Surface Reactions). If you select All, the Reactions list will display all available
reactions. (This option is meant for backward compatibility with FLUENT 6.0 or
earlier cases.)
5. Select the reactions to be included in the mechanism.
For Volumetric or Particle Surface reactions, select available reactions for the
mechanism in the Reactions list.
For Wall Surface reactions, use the following procedure:
(a) Select available wall surface reactions for the mechanism in the Reactions
list.
(b) If any site species appear in the selected reaction(s), set the number of
sites in the Number of Sites eld. (Use the arrows to change the value,
or type the value and press RETURN.) See Section 14.2.2: Wall Surface
Reaction Boundary Conditions for details about site species in wall surface
reactions.
(c) If you specify a Number of Sites that is greater than zero, specify the
properties of the site.
Site Name (optional)
Site Density (in kgmol/m
2
) This value is typically in the range of 10
8
to 10
6
.
Click on the Dene... button. This will open the Site Parameters panel
(Figure 14.1.8), where you will dene the parameters of the site species.
Site Name is the optional name of the site that was specied in the
Reaction Mechanisms panel.
Total Number of Site Species is the number of adsorbed species that are
to be modeled at the site. (Use the arrows to change the value, or
type the value and press RETURN.)
Under Site Species, select the appropriate species from the drop-down
list(s) and specify the fractional Initial Site Coverage for each species.
For steady-state calculations, it is recommended (though not strictly
required) that the initial values of Initial Site Coverage sum to unity.
For transient calculations, it is required that these values sum to unity.
Click Apply in the Site Parameters panel to store the new values.
6. Repeat steps 25 for each reaction mechanism you need to dene. When you are
nished dening all reaction mechanisms, click OK.
Figure 14.1.8: The Site Parameters Panel
Dening Physical Properties for the Mixture
When your FLUENT model includes chemical species, the following physical properties
must be dened, either by you or by the database, for the mixture material:
density, which you can dene using the gas law or as a volume-weighted function
of composition
viscosity, which you can dene as a function of composition
thermal conductivity and specic heat (in problems involving solution of the energy
equation), which you can dene as functions of composition.
mass diusion coecients and Schmidt number, which govern the mass diusion
uxes (Equations 14.1-2 and 14.1-3)
Detailed descriptions of these property inputs are provided in Chapter 8: Physical Properties.
i
Remember to click on the Change/Create button when you are done setting
the properties of the mixture material. The properties that appear for each
of the constituent species will depend on your settings for the properties of
the mixture material. If, for example, you specify a composition-dependent
viscosity for the mixture, you will need to dene viscosity for each species.
Dening Physical Properties for the Species in the Mixture
For each of the uid materials in the mixture, you (or the database) must dene the
following physical properties:
molecular weight, which is used in the gas law and/or in the calculation of reaction
rates and mole-fraction inputs or outputs
standard-state (formation) enthalpy and reference temperature (in problems in-
volving solution of the energy equation)
viscosity, if you dened the viscosity of the mixture material as a function of com-
position
thermal conductivity and specic heat (in problems involving solution of the energy
equation), if you dened these properties of the mixture material as functions of
composition
standard-state entropy, if you are modeling reversible reactions
thermal and momentum accommodation coecients, if you have enabled the low-
pressure boundary slip model.
Detailed descriptions of these property inputs are provided in Chapter 8: Physical Properties.
i
Global reaction mechanisms with one or two steps inevitably neglect the
intermediate species. In high-temperature ames, neglecting these disso-
ciated species may cause the temperature to be overpredicted. A more
realistic temperature eld can be obtained by increasing the specic heat
capacity for each species. Rose and Cooper [308] have created a set of
specic heat polynomials as a function of temperature.
The specic heat capacity for each species is calculated as
c
p
(T) =
m
k=0
a
k
T
k
(14.1-33)
The modied c
p
polynomial coecients (J/kg-K) from [308] are provided in Tables 14.1.1
and 14.1.2.
Table 14.1.1: Modied c
p
Polynomial Coecients (J/kg-K) [308]
N
2
CH
4
CO H
2
a
0
1.02705e+03 2.00500e+03 1.04669e+03 1.4147e+04
a
1
2.16182e02 6.81428e01 1.56841e01 1.7372e01
a
2
1.48638e04 7.08589e03 5.39904e04 6.9e04
a
3
4.48421e08 4.71368e06 3.01061e07
a
4
8.51317e10 5.05048e11
Table 14.1.2: Modied c
p
Polynomial Coecients [308]
CO
2
H
2
O O
2
a
0
5.35446e+02 1.93780e+03 8.76317e+02
a
1
1.27867e+00 1.18077e+00 1.22828e01
a
2
5.46776e04 3.64357e03 5.58304e04
a
3
2.38224e07 2.86327e06 1.20247e06
a
4
1.89204e10 7.59578e10 1.14741e09
a
5
5.12377e13
a
6
8.56597e17
14.1.5 Dening Boundary Conditions for Species
You will need to specify the inlet mass fraction for each species in your simulation. In
addition, for pressure outlets you will set species mass fractions to be used in case of
backow at the exit. At walls, FLUENT will apply a zero-gradient (zero-ux) boundary
condition for all species unless you have dened a surface reaction at that wall (see
Section 14.2: Wall Surface Reactions and Chemical Vapor Deposition), you have dened
a reaction mechanism at that wall (see Section 14.1.4: Dening Zone-Based Reaction
Mechanisms), or you choose to specify species mass fractions at the wall. For uid
zones, you also have the option of specifying a reaction mechanism. Input of boundary
conditions is described in Chapter 7: Boundary Conditions.
i
Non-Reecting Boundary Conditions (NRBCs) are not compatible with
species transport models. They are mainly used to solve ideal-gas single-
specie ow. For information about NRBCs, see section Section 7.23: Non-
Reecting Boundary Conditions.
i
Note that you will explicitly set mass fractions only for the rst N 1
species. The solver will compute the mass fraction of the last species
by subtracting the total of the specied mass fractions from 1. If you
want to explicitly specify the mass fraction of the last species, you must
reorder the species in the list (in the Materials panel), as described in
Section 14.1.4: Dening Properties for the Mixture and Its Constituent
Species.
Diffusion at Inlets with the Pressure-Based Solver
For the pressure-based solver in FLUENT the net transport of species at inlets consists
of both convection and diusion components. The convection component is xed by the
inlet species concentration, whereas the diusion component depends on the gradient of
the computed species concentration eld (which is not known a priori). In some cases,
you may wish to include only the convective transport of species through the inlets of
your domain. You can do this by disabling inlet species diusion. By default, FLUENT
includes the diusion ux of species at inlets. To turn o inlet diusion, use either
the define/models/species/inlet-diffusion? text command, or the Species Model
panel. Generally, you would want to disable the Inlet Diusion option if at one of the
inlets the convective ux is very small, resulting in mass loss by diusion through that
inlet.
Once Species Transport is selected, you can then disable the Inlet Diusion option.
14.1.6 Dening Other Sources of Chemical Species
You can dene a source or sink of a chemical species within the computational domain
by dening a source term in the Fluid panel. You may choose this approach when species
sources exist in your problem but you do not want to model them through the mecha-
nism of chemical reactions. Section 7.28: Dening Mass, Momentum, Energy, and Other
Sources describes the procedures you follow to dene species sources in your FLUENT
model. If the source is not a constant, you can use a user-dened function. See the
separate UDF Manual for details about user-dened functions.
14.1.7 Solution Procedures for Chemical Mixing and Finite-Rate Chemistry
While many simulations involving chemical species may require no special procedures
during the solution process, you may nd that one or more of the solution techniques
noted in this section helps to accelerate the convergence or improve the stability of more
complex simulations. The techniques outlined below may be of particular importance if
your problem involves many species and/or chemical reactions, especially when modeling
combusting ows.
Stability and Convergence in Reacting Flows
Obtaining a converged solution in a reacting ow can be dicult for a number of reasons.
First, the impact of the chemical reaction on the basic ow pattern may be strong, leading
to a model in which there is strong coupling between the mass/momentum balances and
the species transport equations. This is especially true in combustion, where the reactions
lead to a large heat release and subsequent density changes and large accelerations in
the ow. All reacting systems have some degree of coupling, however, when the ow
properties depend on the species concentrations. These coupling issues are best addressed
by the use of a two-step solution process, as described below, and by the use of under-
relaxation as described in Section 25.9.2: Setting Under-Relaxation Factors.
A second convergence issue in reacting ows involves the magnitude of the reaction source
term. When the FLUENT model involves very rapid reaction rates (reaction time scales
are much faster than convection and diusion time scales), the solution of the species
transport equations becomes numerically dicult. Such systems are termed sti sys-
tems. Sti systems with laminar chemistry can be solved using either the pressure-based
solver with the Sti Chemistry Solver option enabled, or the density-based solver (see
Section 14.1.7: Solution of Sti Laminar Chemistry Systems). The laminar chemistry
model may also be used for turbulent ames, where turbulence-chemistry interactions
are neglected. However, for such ames, the EDC or PDF Transport models, which
account for turbulence-chemistry interactions, may be a better choice.
Two-Step Solution Procedure (Cold Flow Simulation)
Solving a reacting ow as a two-step process can be a practical method for reaching
a stable converged solution to your FLUENT problem. In this process, you begin by
solving the ow, energy, and species equations with reactions disabled (the cold-ow,
or unreacting ow). When the basic ow pattern has thus been established, you can re-
enable the reactions and continue the calculation. The cold-ow solution provides a good
starting solution for the calculation of the combusting system. This two-step approach
to combustion modeling can be accomplished using the following procedure:
1. Set up the problem including all species and reactions of interest.
2. Temporarily disable reaction calculations by turning o Volumetric in the Species
Model panel.
3. Turn o calculation of the product species in the Solution Controls panel.
Solve Controls Solution...
4. Calculate an initial (cold-ow) solution. (Note that it is generally not productive
to obtain a fully converged cold-ow solution unless the non-reacting solution is
also of interest to you.)
5. Enable the reaction calculations by turning on Volumetric again in the Species Model
panel.
6. Turn on all equations. If you are using the laminar nite-rate, nite-rate/eddy-
dissipation, EDC or PDF Transport model for turbulence-chemistry interaction,
you may need to patch an ignition source (as described below).
Density Under-Relaxation
One of the main reasons a combustion calculation can have diculty converging is that
large changes in temperature cause large changes in density, which can, in turn, cause
instabilities in the ow solution. When you use the pressure-based solver, FLUENT allows
you to under-relax the change in density to alleviate this diculty. The default value for
density under-relaxation is 1, but if you encounter convergence trouble you may wish to
reduce this to a value between 0.5 and 1 (in the Solution Controls panel).
Ignition in Combustion Simulations
If you introduce fuel to an oxidant, spontaneous ignition does not occur unless the tem-
perature of the mixture exceeds the activation energy threshold required to maintain
combustion. This physical issue manifests itself in a FLUENT simulation as well. If you
are using the laminar nite-rate, nite-rate/eddy-dissipation, EDC or PDF Transport
model for turbulence-chemistry interaction, you have to supply an ignition source to ini-
tiate combustion. This ignition source may be a heated surface or inlet mass ow that
heats the gas mixture above the required ignition temperature. Often, however, it is the
equivalent of a spark: an initial solution state that causes combustion to proceed. You
can supply this initial spark by patching a hot temperature into a region of the FLUENT
model that contains a sucient fuel/air mixture for ignition to occur.
Solve Initialize Patch...
Depending on the model, you may need to patch both the temperature and the fuel/
oxidant/product concentrations to produce ignition in your model. The initial patch
has no impact on the nal steady-state solutionno more than the location of a match
determines the nal ow pattern of the torch that it lights. See Section 25.14.2: Patching
Values in Selected Cells for details about patching initial values.
Solution of Stiff Laminar Chemistry Systems
When modeling sti laminar ames with the laminar nite-rate model, you can either
use the pressure-based solver with the Sti Chemistry Solver option enabled as seen in the
Species Model panel (Figure 14.1.1), or the density-based solver.
When using the pressure-based solver for unsteady simulations, the Sti Chemistry Solver
option applies a fractional step algorithm. In the rst fractional step, the chemistry in
each cell is reacted at constant pressure for the ow time-step, using the ISAT integrator.
In the second fractional step, the convection and diusion terms are treated just as in a
non-reacting simulation.
For steady simulations using the pressure-based solver, the Sti Chemistry Solver option
approximates the reaction rate R
i
in the species transport equation (see Equation 14.1-5)
as,
R
i
=
1
_

0
R
i
dt (14.1-34)
where is some time-step that requires careful selection. Note that as tends to zero
the approximation becomes exact but the sti numerics will cause the pressure-based
solver to diverge. On the other hand, as tends to innity, the approximated reaction
rate R
i
tends to zero and, while the numerical stiness is alleviated, there is no reaction.
In FLUENT, the default value for is set to one-tenth of the minimum convective or
diusive time-scale in the cell. This value was found to be suciently accurate and
robust, although it can be modied via the solve/set/stiff-chemistry text command.
ISAT is employed to integrate the sti chemistry in Equation 14.1-34.
Details about the ISAT algorithm may be found in Sections 18.2.4 and Section 18.3.9: Us-
ing ISAT Eciently. For ecient and accurate use of ISAT, a review of this section is
highly recommended.
Choosing the density-based implicit solver can provide further solution stability by en-
abling the Sti Chemistry Solver option. This option allows a larger stable Courant
(CFL) number specication, although additional calculations are required to calculate
the eigenvalues of the chemical Jacobian [392]. When enabling the sti-chemistry solver,
the following must be specied:
Temperature Positivity Rate Limit: limits new temperature changes by this factor
multiplied by the old temperature. Its default value is 0.2.
Temperature Time Step Reduction: limits the local CFL number when the temper-
ature is changing too rapidly. Its default value is 0.25.
Max. Chemical Time Step Ratio: limits the local CFL number when the chemical
time scales (eigenvalues of the chemical Jacobian) become too large to maintain a
well-conditioned matrix. Its default value is 0.9.
If the density-based explicit solver is used, then the stiff-chemistry solver has to be
enabled via the text command:
solve set stiff-chemistry
You will be prompted to specify the following:
Positivity Rate Limit (for temperature): limits new temperature changes by this
factor multiplied by the old temperature. Its default value is 0.2.
Temperature time-step reduction factor: limits the local CFL number when the
temperature is changing too rapidly. Its default value is 0.25.
Maximum allowable time-step/chemical-time-scale ratio: limits the local CFL num-
ber when the chemical time scales (eigenvalues of the chemical Jacobian) become
too large to maintain a well-conditioned matrix. Its default value is 0.9.
The default values of these parameters are applicable in most cases.
EDC Model Solution Procedure
Due to the high computational expense of the EDC model, it is recommended that you
use the following procedure to obtain a solution using the pressure-based solver:
1. Calculate an initial solution using the equilibrium Non-premixed or Partially-premixed
model (see Chapters 15 and 17).
2. Import a CHEMKIN format reaction mechanism (see Section 14.1.9: Importing a
Volumetric Kinetic Mechanism in CHEMKIN Format).
3. Enable the reaction calculations by turning on Volumetric Reactions in the Species
Model panel and selecting EDC under Turbulence-Chemistry Interaction. Select the
mechanism that you just imported as the Mixture Material.
Dene Models Species...
4. Set the species boundary conditions.
Dene Boundary Conditions...
5. Disable the ow and turbulence and solve for the species and temperature only.
6. Enable all equations and iterate to convergence. Note that the default numerical
parameters for the solution of the EDC equations are set to provide maximum
robustness with slowest convergence. The convergence rate can be increased by
setting the Acceleration Factor with the text command:
define/models/species/set-turb-chem-interaction
The Acceleration Factor can be set from 0 (slow but stable) to 1 (fast but
unstable).
14.1.8 Postprocessing for Species Calculations
FLUENT can report chemical species as mass fractions, mole fractions, and molar con-
centrations. You can also display laminar and eective mass diusion coecients. The
following variables are available for postprocessing of species transport and reaction sim-
ulations:
Mass fraction of species-n
Mole fraction of species-n
Molar Concentration of species-n
Lam Di Coef of species-n
E Di Coef of species-n
Thermal Di Coef of species-n
Enthalpy of species-n (pressure-based solver calculations only)
species-n Source Term (density-based solver calculations only)
Relative Humidity
Time Step Scale (sti-chemistry solver only)
Fine Scale Mass fraction of species-n (EDC model only)
Fine Scale Transfer Rate (EDC model only)
1-Fine Scale Volume Fraction (EDC model only)
Fine Scale Temperature (EDC model only)
Rate of Reaction-n
Arrhenius Rate of Reaction-n
Turbulent Rate of Reaction-n
These variables are contained in the Species..., Temperature..., and Reactions... categories
of the variable selection drop-down list that appears in postprocessing panels. See Chap-
ter 30: Field Function Denitions for a complete list of ow variables, eld functions,
and their denitions. Chapters 28 and 29 explain how to generate graphics displays and
reports of data.
Averaged Species Concentrations
Averaged species concentrations at inlets and exits, and across selected planes (i.e., sur-
faces that you have created using the Surface menu items) within your model can be ob-
tained using the Surface Integrals panel, as described in Section 29.5: Surface Integration.
Report Surface Integrals...
Select the Molar Concentration of species-n for the appropriate species in the Field Variable
drop-down list.
14.1.9 Importing a Volumetric Kinetic Mechanism in CHEMKIN Format
If you have a gas phase chemical mechanism in CHEMKIN format, you can import the
mechanism le into FLUENT using the CHEMKIN Mechanism Import panel (Figure 14.1.9).
File Import CHEMKIN Mechanism...
Figure 14.1.9: The CHEMKIN Mechanism Import Panel for Volumetric Kinet-
ics
In the CHEMKIN Mechanism Import panel
1. Enter a name for the chemical mechanism under Material Name.
2. Enter the path to the CHEMKIN le (e.g., path/file.che) under Gas Phase CHEMKIN
Mechanism File.
3. Specify the location of the Gas Phase Thermodynamic Data File (thermo.db). The
format for thermo.db is detailed in the CHEMKIN manual [177]. The default
thermo.db le in CHEMKIN is available only for gas phase species.
4. (Optional). Import transport properties by enabling the Import Transport Property
Database and entering the path to that le. If you want to use KINetics transport
properties, you must rst enable the KINetics from Reaction Design option in the
Species panel (Figure 14.1.1). Once a le with KINetics transport properties is
read, FLUENT will create a material with the specied name, which will contain
the data for the species and reactions, and add it to the list of available Mixture
Materials in the Materials panel. For material properties such as Viscosity, Thermal
Conductivity, Mass Diusivity, and Thermal Diusion, listed in the Materials panel,
the option reaction-design will appear in the drop-down list of each of the prop-
erties (Figure 14.1.10), allowing you to use material property values computed by
KINetics.
Note that when Full Multicomponent Diusion is enabled in the Species panel, KI-
Netics returns full multicomponent diusivities. If Full Multicomponent Diusion is
disabled, KINetics returns mixture averaged mass diusivities for each species.
Note that since FLUENT does not solve for the last species, you should ensure that
the last species in the CHEMKIN mechanism species list is the bulk species. If not,
edit the CHEMKIN mechanism le before importing it into FLUENT, and move
the bulk species (i.e. the species in your system with the largest total mass) to the
end of the species list.
5. Click the Import button.
i
Note that the CHEMKIN import facility does not provide full compatibility
with all CHEMKIN rate formulations and that to access more complete
functionality, you should consider the KINetics module option described
in Section 14.1.3: Enabling Species Transport and Reactions and Choosing
the Mixture Material
For information on importing a surface kinetic mechanism in CHEMKIN format, see
Section 14.2.6: Importing a Surface Kinetic Mechanism in CHEMKIN Format.
Figure 14.1.10: The Material Panel When Importing CHEMKIN Transport
Properties
14.2 Wall Surface Reactions and Chemical Vapor Deposition
For gas-phase reactions, the reaction rate is dened on a volumetric basis and the rate
of creation and destruction of chemical species becomes a source term in the species
conservation equations. The rate of deposition is governed by both chemical kinetics and
the diusion rate from the uid to the surface. Wall surface reactions thus create sources
(and sinks) of chemical species in the bulk phase and determine the rate of deposition of
surface species.
Information about wall surface reactions and chemical vapor deposition is presented in
the following subsections:
Section 14.2.1: Overview of Surface Species and Wall Surface Reactions
Section 14.2.3: User Inputs for Wall Surface Reactions
Section 14.2.4: Solution Procedures for Wall Surface Reactions
Section 14.2.5: Postprocessing for Surface Reactions
14.2.1 Overview of Surface Species and Wall Surface Reactions
FLUENT treats chemical species deposited on surfaces as distinct from the same chemical
species in the gas. Similarly, reactions involving surface deposition are dened as distinct
surface reactions and hence treated dierently than bulk phase reactions involving the
same chemical species.
Surface reactions can be limited so that they occur on only some of the wall boundaries
(while the other wall boundaries remain free of surface reaction). The surface reaction
rate is dened and computed per unit surface area, in contrast to the uid-phase reactions,
which are based on unit volume.
14.2.2 Theory
Consider the rth wall surface reaction written in general form as follows:
Ng
i=1
g
i,r
G
i
+
N
b
i=1
b
i,r
B
i
+
Ns
i=1
s
i,r
S
i
Kr
Ng
i=1
g
i,r
G
i
+
N
b
i=1
b
i,r
B
i
+
Ns
i=1
s
i,r
S
i
(14.2-1)
where G
i
, B
i
, and S
i
represent the gas phase species, the bulk (or solid) species, and the
surface-adsorbed (or site) species, respectively. N
g
, N
b
, and N
s
are the total numbers of
these species. g
i,r
, b
i,r
, and s
i,r
are the stoichiometric coecients for each reactant species
i, and g
i,r
, b
i,r
, and s
i,r
are the stoichiometric coecients for each product species i. K
r
is the overall reaction rate constant.
The summations in Equation 14.2-1 are for all chemical species in the system, but only
species involved as reactants or products will have non-zero stoichiometric coecients.
Hence, species that are not involved will drop out of the equation.
The rate of the rth reaction is
R
r
= k
f,r
Ng
i=1
[G
i
]
g
i,r
wall
[S
i
]
s
i,r
wall
(14.2-2)
where [ ]
wall
represents molar concentrations on the wall. It is assumed that the reaction
rate does not depend on concentrations of the bulk (solid) species. From this, the net
molar rate of production or consumption of each species i is given by
R
i,gas
=
Nrxn
r=1
(g
i,r
g
i,r
)R
r
i = 1, 2, 3, . . . , N
g
(14.2-3)
R
i,bulk
=
Nrxn
r=1
(b
i,r
b
i,r
)R
r
i = 1, 2, 3, . . . , N
b
(14.2-4)
R
i,site
=
Nrxn
r=1
(s
i,r
s
i,r
)R
r
i = 1, 2, 3, . . . , N
s
(14.2-5)
The forward rate constant for reaction r (k
f,r
) is computed using the Arrhenius expres-
sion. For example,
k
f,r
= A
r
T
r
e
Er/RT
(14.2-6)
where A
r
= pre-exponential factor (consistent units)
r
= temperature exponent (dimensionless)
E
r
= activation energy for the reaction (J/kgmol)
R = universal gas constant (J/kgmol-K)
You (or the database) will provide values for g
i,r
, g
i,r
, b
i,r
, b
i,r
, s
i,r
, s
i,r
,
r
, A
r
, and E
r
.
Wall Surface Reaction Boundary Conditions
As shown in Equations 14.2-214.2-5, the goal of surface reaction modeling is to com-
pute concentrations of gas species and site species at the wall; i.e., [G
i
]
wall
and [S
i
]
wall
.
Assuming that, on a reacting surface, the mass ux of each gas species is balanced with
its rate of production/consumption, then
wall
D
i
Y
i,wall
n
m
dep
Y
i,wall
= M
w,i

R
i,gas
i = 1, 2, 3, . . . , N
g
(14.2-7)
[S
i
]
wall
t
=

R
i,site
i = 1, 2, 3, . . . , N
s
(14.2-8)
The mass fraction Y
i,wall
is related to concentration by
[G
i
]
wall
=

wall
Y
i,wall
M
w,i
(14.2-9)
m
dep
is the net rate of mass deposition or etching as a result of surface reaction; i.e.,
m
dep
=
N
b
i=1
M
w,i

R
i,bulk
(14.2-10)
[S
i
]
wall
is the site species concentration at the wall, and is dened as
[S
i
]
wall
=
site
z
i
(14.2-11)
where
site
is the site density and z
i
is the site coverage of species i.
Using Equations 14.2-7 and 14.2-8, expressions can be derived for the mass fraction of
species i at the wall and for the net rate of creation of species i per unit area. These
expressions are used in FLUENT to compute gas phase species concentrations, and if
applicable, site coverages, at reacting surfaces using a point-by-point coupled sti solver.
Including Mass Transfer To Surfaces in Continuity
In the surface reaction boundary condition described above, the eects of the wall normal
velocity or bulk mass transfer to the wall are not included in the computation of species
transport. The momentum of the net surface mass ux from the surface is also ignored
because the momentum ux through the surface is usually small in comparison with the
momentum of the ow in the cells adjacent to the surface. However, you can include the
eect of surface mass transfer in the continuity equation by activating the Mass Deposition
Source option in the Species Model panel.
Wall Surface Mass Transfer Effects in the Energy Equation
Species diusion eects in the energy equation due to wall surface reactions are included
in the normal species diusion term described in Section 14.1.1: Treatment of Species
Transport in the Energy Equation.
If you are using the pressure-based solver, you can neglect this term by turning o
the Diusion Energy Source option in the Species Model panel. (For the density-based
solvers, this term is always included; you cannot turn it o.) Neglecting the species
diusion term implies that errors may be introduced to the prediction of temperature in
problems involving mixing of species with signicantly dierent heat capacities, especially
for components with a Lewis number far from unity. While the eect of species diusion
should go to zero at Le = 1, you may see subtle eects due to dierences in the numerical
integration in the species and energy equations.
Modeling the Heat Release Due to Wall Surface Reactions
The heat release due to a wall surface reaction is, by default, ignored by FLUENT. You
can, however, choose to include the heat of surface reaction by activating the Heat of
Surface Reactions option in the Species Model panel and setting appropriate formation
enthalpies in the Materials panel.
Slip Boundary Formulation for Low-Pressure Gas Systems
Most semiconductor fabrication devices operate far below atmospheric pressure, typically
only a few millitorrs. At such low pressures, the uid ow is in the slip regime and the
normally used no-slip boundary conditions for velocity and temperature are no longer
valid.
Knudsen number, Kn, which is dened as the ratio of mean free path to a characteristic
length scale of the system, is used to describe various ow regimes. Since the mean
free path increases as the pressure is lowered, the high end of Kn values represents free
molecular ow and the low end the continuum regime. The range in between these two
extremes is called the slip regime (0.001 < Kn < 0.1).
In the slip regime, the gas-phase velocity at a solid surface diers from the velocity
at which the wall moves, and the gas temperature at the surface diers from the wall
temperature. Maxwells models are adopted for these physical phenomena in FLUENT
for their simplicity and eectiveness.
velocity slip
U
w
U
g
=
_
2
v
v
_
Kn
U
n

_
2
v
v
_
(U
g
U
c
) (14.2-12)
V
g
(
V n)
g
= V
w
(14.2-13)
Here, U and V represents the velocity component that is parallel and normal to
the wall, respectively. The subscripts g, w and c indicate gas, wall and cell-center
velocities. is the distance from cell center to the wall.
v
is the momentum
accommodation coecient of the gas mixture and its value is calculated as mass-
fraction weighted average of each gas species in the system.
v
=
Ng
i=1
Y
i
i
(14.2-14)
The mean free path, , is computed as follows:
=
k
B
T
2
2
p
(14.2-15)
=
Ng
i=1
Y
i
i
(14.2-16)
i
is the Lennard-Jones characteristic length of species i. k
B
is the Boltzmann
constant, 1.38066 10
23
J/K.
Equations 14.2-12 and 14.2-13 indicate that while the gas velocity component nor-
mal to the wall is the same as the wall normal velocity, the tangential components
slip. The values lie somewhere between the cell-center and the wall values. These
two equations can be combined to give a generalized formulation:
V
g
=
V
w
+
k
[(
V
w
n)n +

V
c
(
V
c
n)n]
1 +
k
(14.2-17)
where
k
_
2
v
v
_
(14.2-18)
temperature jump
T
w
T
g
= 2
_
2
T
T
_
Kn
T
n
2
_
2
T
T
_
(T
g
T
c
) (14.2-19)
or equivalently
T
g
=
T
w
+ T
c
1 +
(14.2-20)
where
=
2(2
T
)
(14.2-21)
T
is the thermal accommodation coecient of the gas mixture and is calculated
as
T
=
Y
i
T,i
.
i
The low-pressure slip boundary formulation is available only with the
pressure-based solver.
14.2.3 User Inputs for Wall Surface Reactions
The basic steps for setting up a problem involving wall surface reactions are the same as
those presented in Section 14.1.2: Overview of User Inputs for Modeling Species Trans-
port and Reactions for setting up a problem with only uid-phase reactions, with a few
additions:
1. In the Species Model panel:
(a) Enable Species Transport, select Volumetric and Wall Surface under Reactions,
and specify the Mixture Material. See Section 14.1.3: Enabling Species Trans-
port and Reactions and Choosing the Mixture Material for details about this
procedure, and Section 14.1.2: Mixture Materials for an explanation of the
mixture material concept.
(b) (optional) If you want to model the heat release due to wall surface reactions,
turn on the Heat of Surface Reactions option.
(c) (optional) If you want to include the eect of surface mass transfer in the
continuity equation, turn on the Mass Deposition Source option.
(d) (optional) If you are using the pressure-based solver and you do not want to
include species diusion eects in the energy equation, turn o the Diusion
Energy Source option. See Section 14.2.2: Wall Surface Mass Transfer Eects
in the Energy Equation for details.
(e) (optional, but recommended for CVD) If you want to model full multicompo-
nent diusion or thermal diusion, turn on the Full Multicomponent Diusion
or Thermal Diusion option. See Section 8.9.2: Full Multicomponent Diusion
for details.
2. Check and/or dene the properties of the mixture. (See Section 14.1.4: Dening
Properties for the Mixture and Its Constituent Species.)
Dene Materials...
Mixture properties include the following:
reactions
i
You will nd all species (including the solid/bulk and site species) in the
list of Fluent Fluid Materials. For a species such as Si, you will nd both
Si(g) and Si(s) in the materials list for the uid material type.
Note that if you were modeling the silicon deposition reactions in the example
at the beginning of Section 14.2.1: Overview of Surface Species and Wall Surface
Reactions, you would need to include both Si species (gas and solid) in the mixture.
i
Note that the nal gas phase species named in the Selected Species list
should be the carrier gas if your model includes species in dilute mixtures.
(This is because FLUENT will not solve the transport equation for the
nal species.) Note also that any reordering, adding or deleting of species
should be handled with caution, as described in Section 14.1.4: Reordering
Species.
3. Check and/or set the properties of the individual species in the mixture. (See
Section 14.1.4: Dening Properties for the Mixture and Its Constituent Species.)
Note that if you are modeling the heat of surface reactions, you should be sure to
check (or dene) the formation enthalpy for each species.
4. Set species boundary conditions.
Dene Boundary Conditions...
In addition to the boundary conditions described in Section 14.1.5: Dening Bound-
ary Conditions for Species, you will rst need to indicate whether or not surface
reactions are in eect on each wall. If so, you will then need to assign a reaction
mechanism to the wall. To enable the eect of surface reaction on a wall, turn on
the Reaction option in the Species section of the Wall panel.
i
If you have enabled the global Low-Pressure Boundary Slip option in the
Viscous Model panel, the Shear Condition for each wall will be reset to No
Slip even though the slip model will be in eect. Note that the Low-Pressure
Boundary Slip option is available only when the Laminar model is selected
in the Viscous Model panel.
See Section 7.13.1: Inputs at Wall Boundaries for details about boundary condition
inputs for walls. See Section 7.19.6: User Inputs for Porous Media for details about
boundary condition inputs for porous media.
14.2.4 Solution Procedures for Wall Surface Reactions
As in all CFD simulations, your surface reaction modeling eort may be more successful if
you start with a simple problem description, adding complexity as the solution proceeds.
For wall surface reactions, you can follow the same guidelines presented for uid-phase
reactions in Section 14.1.7: Solution Procedures for Chemical Mixing and Finite-Rate
Chemistry.
In addition, if you are modeling the heat release due to surface reactions and you are
having convergence trouble, you should try temporarily turning o the Heat of Surface
Reactions and Mass Deposition Source options in the Species Model panel.
14.2.5 Postprocessing for Surface Reactions
In addition to the variables listed in Section 14.1.8: Postprocessing for Species Calculations,
for surface reactions you can also display/report the surface coverage as well as the depo-
sition rate of the solid species deposited on a surface. Select Surface Coverage of species-n
or Surface Deposition Rate of species-n in the Species... category of the variable selection
drop-down list.
i
For surface reactions involving porous media, you can display/report the
surface reaction rates using the Arrhenius Rate of Reaction-n in the Reac-
tions... category of the variable selection drop-down list.
14.2.6 Importing a Surface Kinetic Mechanism in CHEMKIN Format
Importing surface kinetic mechanisms in CHEMKIN format (Section 14.1.9: Importing a
Volumetric Kinetic Mechanism in CHEMKIN Format) requires that the gas phase mech-
anism le accompany the surface mechanism le for full compatibility with CHEMKIN.
If the gas phase mechanism le is not available, then you will need to create one that
you will import along with the surface mechanism le. The mechanism les are imported
into FLUENT using the CHEMKIN Mechanism Import panel (Figure 14.2.1).
File Import CHEMKIN Mechanism...
Figure 14.2.1: The CHEMKIN Mechanism Import Panel for Surface Kinetics
In the CHEMKIN Mechanism Import panel
1. Enter a name for the chemical mechanism under Material Name.
2. Enable Import Surface CHEMKIN Mechanism.
3. Enter the path to the Gas Phase CHEMKIN Mechanism File (e.g., path/gas-file.che)
and the Surface CHEMKIN Mechanism File (e.g., path/surface-file.che).
4. Specify the location of the Thermodynamic Data File (thermo.db). The format for
thermo.db is detailed in the CHEMKIN Users Guide [177]. The default thermo.db
le supplied with FLUENT has only gas phase species available. You will need to
supply a surface thermo.db le for your surface species if this thermo information
is not in the mechanism le.
i
Note that FLUENT will initially search for the thermodynamic data in
the Surface CHEMKIN Mechanism File. If the data does not exist in the
mechanism le, then FLUENT will search for the thermodynamic data in
the specied Thermodynamic Database File.
5. (Optional). Import transport properties by enabling the Import Transport Property
Database and entering the path to that le.
To read in KINetics transport properties, go to Section 14.1.9: Importing a Volu-
metric Kinetic Mechanism in CHEMKIN Format for detailed information.
6. Click the Import button.
FLUENT will create a material with the specied name, which will contain the CHEMKIN
data for the species and reactions, and add it to the list of Fluent Mixture Materials. You
can view all of the reactions by clicking on the Edit... button to the right of Mechanism,
under Properties in the Materials panel.
Note that for surface reaction mechanisms, the surface reaction rate constant can be
expressed in terms of a sticking coecient. FLUENT will convert this sticking coecient
form to the Arrhenius rate expression [176].
i
The CHEMKIN import facility does not provide full compatibility with
all CHEMKIN rate formulations. To access more complete functional-
ity, you should consider the KINetics module option described in Sec-
tion 14.1.3: Enabling Species Transport and Reactions and Choosing the
Mixture Material.
Compatibility and Limitations for Gas Phase Reactions
FLUENT will allow for the following reaction types:
Arrhenius reactions with arbitrary reaction order, third-body eciencies and non-
integer stoichiometric coecients.
Pressure dependent reactions (Lindemann, Troe and SRI forms)
Arbitrary reaction units
Duplicate reactions (keyword DUP)
FLUENT will not allow for the following reaction types:
Landau-Teller reactions (keyword LT)
Reverse Landau-Teller reactions (keyword RLT)
Janev reactions (keyword JAN)
Exponential modied power series reactions(keyword FIT1)
Radiation reactions (keyword HV)
Energy loss reactions (keyword EXCI)
Multi-uid temperature dependence reactions (keyword TDEP)
Electron momentum transfer collision frequency (keyword MOME)
Arbitrary reverse reaction (keyword REV)
i
Note that the reaction types that FLUENT will not allow are mostly appli-
cable to plasmas.
Compatibility and Limitations for Surface Reactions
FLUENT will allow for the following reaction types:
Arrhenius reactions with arbitrary reaction order, third-body eciencies and non-
integer stoichiometric coecients.
Sticking coecients (keyword STICK). Fluent converts these to an equivalent Ar-
rhenius expression.
Arbitrary reaction units
Duplicate reactions (keyword DUP)
FLUENT will not allow for the following reaction types:
Surface Coverage modication (keyword COV)
Ion-Energy Dependent reaction (keyword ENRGDEP)
Bohm rate expressions (keyword BOHM)
Ion-Enhanced reaction
Motz-Wise correction (keywords MWON and MWOFF)
i
FLUENT will warn you of any incompatibilities.
For a detailed description of the keywords, see [176].
14.3 Particle Surface Reactions
As described in Section 22.9.2: The Multiple Surface Reactions Model, it is possible to
dene multiple particle surface reactions to model the surface combustion of a combusting
discrete-phase particle. Information about particle surface reactions is provided in the
following subsections:
Section 14.3.2: User Inputs for Particle Surface Reactions
Section 14.3.3: Using the Multiple Surface Reactions Model for Discrete-Phase Par-
ticle Combustion
14.3.1 Theory
General Description
The relationships for calculating char particle burning rates are presented and discussed
in detail by Smith [341]. The particle reaction rate, R (kg/m
2
-s), can be expressed as
R = D
0
(C
g
C
s
) = R
c
(C
s
)
N
(14.3-1)
where
D
0
= bulk diusion coecient (m/s)
C
g
= mean reacting gas species concentration in the bulk (kg/m
3
)
C
s
= mean reacting gas species concentration at the particle surface (kg/m
3
)
R
c
= chemical reaction rate coecient (units vary)
N = apparent reaction order (dimensionless)
In Equation 14.3-1, the concentration at the particle surface, C
s
, is not known, so it
should be eliminated, and the expression is recast as follows:
R = R
c
_
C
g
R
D
0
_
N
(14.3-2)
This equation has to be solved by an iterative procedure, with the exception of the cases
when N = 1 or N = 0. When N = 1, Equation 14.3-2 can be written as
R =
C
g
R
c
D
0
D
0
+ R
c
(14.3-3)
In the case of N = 0, if there is a nite concentration of reactant at the particle surface,
the solid depletion rate is equal to the chemical reaction rate. If there is no reactant
at the surface, the solid depletion rate changes abruptly to the diusion-controlled rate.
In this case, however, FLUENT will always use the chemical reaction rate for stability
reasons.
FLUENT Model Formulation
A particle undergoing an exothermic reaction in the gas phase is shown schematically in
Figure 14.3.1. T
p
and T
are the temperatures in Equation 22.9-86.

C
C
C
T
T
d,b
d,s
k
p
Distance
T
e
m
p
e
r
a
t
u
r
e
C
o
n
c
e
n
t
r
a
t
i
o
n
Figure 14.3.1: A Reacting Particle in the Multiple Surface Reactions Model
Based on the analysis above, FLUENT uses the following equation to describe the rate
of reaction r of a particle surface species j with the gas phase species n. The reaction
stoichiometry of reaction r in this case is described by
particle species j(s) + gas phase species n products
and the rate of reaction is given as
R
j,r
= A
p
r
Y
j
R
j,r
(14.3-4)
R
j,r
= R
kin,r
_
p
n
R
j,r
D
0,r
_
N
(14.3-5)
where
R
j,r
= rate of particle surface species depletion (kg/s)
A
p
= particle surface area (m
2
)
Y
j
= mass fraction of surface species j in the particle
r
= eectiveness factor (dimensionless)
R
j,r
= rate of particle surface species reaction per unit area (kg/m
2
-s)
p
n
= bulk partial pressure of the gas phase species (Pa)
D
0,r
= diusion rate coecient for reaction r
R
kin,r
= kinetic rate of reaction r (units vary)
N
r
= apparent order of reaction r
The eectiveness factor,
r
, is related to the surface area, and can be used in each reaction
in the case of multiple reactions. D
0,r
is given by
D
0,r
= C
1,r
[(T
p
+ T
)/2]
0.75
d
p
(14.3-6)
The kinetic rate of reaction r is dened as
R
kin,r
= A
r
T
r
e
(Er/RT)
(14.3-7)
The rate of the particle surface species depletion for reaction order N
r
= 1 is given by
R
j,r
= A
p
r
Y
j
p
n
R
kin,r
D
0,r
D
0,r
+R
kin,r
(14.3-8)
For reaction order N
r
= 0,
R
j,r
= A
p
r
Y
j
R
kin,r
(14.3-9)
Extension for Stoichiometries with Multiple Gas Phase Reactants
When more than one gas phase reactant takes part in the reaction, the reaction stoi-
chiometry must be extended to account for this case:
particle species j(s) + gas phase species 1 + gas phase species 2 + . . .
+ gas phase species n
max
products
To describe the rate of reaction r of a particle surface species j in the presence of n
max
gas phase species n, it is necessary to dene the diusion-limited species for each solid
particle reaction, i.e., the species for which the concentration gradient between the bulk
and the particle surface is the largest. For the rest of the species, the surface and the
bulk concentrations are assumed to be equal. The concentration of the diusion-limited
species is shown as C
d,b
and C
d,s
in Figure 14.3.1, and the concentrations of all other
species are denoted as C
k
. For stoichiometries with multiple gas phase reactants, the
bulk partial pressure p
n
in Equations 14.3-4 and 14.3-8 is the bulk partial pressure of the
diusion-limited species, p
r,d
for reaction r.
The kinetic rate of reaction r is then dened as
R
kin,r
=
A
r
T
r
e
(Er/RT)
(p
r,d
)
N
r,d
nmax
n=1
p
Nr,n
n
(14.3-10)
where
p
n
= bulk partial pressure of gas species n
N
r,n
= reaction order in species n
When this model is enabled, the constant C
1,r
(Equation 14.3-6) and the eectiveness
factor
r
(Equation 14.3-4) are entered in the Reactions panel, as described in Sec-
tion 14.3.2: User Inputs for Particle Surface Reactions.
Solid-Solid Reactions
Reactions involving only particle surface reactants can be modeled, provided that the
particle surface reactants and products exist on the same particle.
particle species 1(s) + particle species 2(s) + . . . products
The reaction rate for this case is given by Equation 14.3-9.
Solid Decomposition Reactions
The decomposition reactions of particle surface species can be modeled.
particle species 1(s) + particle species 2(s) + . . . + particle species n
max
(s)
gas species j + products
The reaction rate for this case is given by Equations 14.3-414.3-10, where the diusion-
limited species is now the gaseous product of the reaction. If there are more than one
gaseous product species in the reaction, it is necessary to dene the diusion-limited
species for the particle reaction as the species for which the concentration gradient be-
tween the bulk and the particle surface is the largest.
Solid Deposition Reactions
The deposition reaction of a solid species on a particle can be modeled with the following
assumptions:
gas species 1 + gas species 2 + . . . + gas species n
max
solid species j(s) + products
The theoretical analysis and Equations 14.3-414.3-10 are applied for the surface re-
action rate calculation, with the mass fraction of the surface species set to unity in
Equations 14.3-4, 14.3-8, and 14.3-9.
In FLUENT, for the particle surface species to be deposited on a particle, a nite mass
of the species must already exist in the particle. This allows for activation of the depo-
sition reaction selectively to particular injection particles. It follows that, to initiate the
solid species deposition reaction on a particle, the particle must be dened in the Set
Injection Properties panel (or Set Multiple Injection Properties panel) to contain a small
mass fraction of the solid species to be deposited. See Section 14.3.3: Using the Multiple
Surface Reactions Model for Discrete-Phase Particle Combustion for details on dening
the particle surface species mass fractions.
Gaseous Solid Catalyzed Reactions on the Particle Surface
Reactions of gaseous species catalyzed on the particle surface can also be modeled fol-
lowing Equations 14.3-414.3-10 for the surface reaction rate calculation, with the mass
fraction of the surface species set to unity in Equations 14.3-4, 14.3-8, and 14.3-9.
The catalytic particle surface reaction option is enabled in FLUENT when Particle Surface
is selected as the Reaction Type in the Reactions panel and there are no solid species in
the reaction stoichiometry. The solid species acting as a catalyst for the reaction is
dened in the Reactions panel. The catalytic particle surface reaction will proceed only
on those particles containing the catalyst species. See Section 14.3.3: Using the Multiple
Surface Reactions Model for Discrete-Phase Particle Combustion for details on dening
the particle surface species mass fractions.
14.3.2 User Inputs for Particle Surface Reactions
The setup procedure for particle surface reactions requires only a few inputs in addition
to the procedure for volumetric reactions described in Sections 14.1.214.1.6. These
additional inputs are as follows:
In the Species Model panel, turn on the Particle Surface option under Reactions.
When you specify the species involved in the particle surface reaction, be sure to
identify the surface species, as described in Section 14.1.4: Dening Properties for
the Mixture and Its Constituent Species.
i
You will nd all species (including the surface species) in the list of Fluent
Fluid Materials. If, for example, you are modeling coal gasication, you will
nd solid carbon, C(s), in the materials list for the uid material type.
For each particle surface reaction, select Particle Surface as the Reaction Type in
the Reactions panel, and specify the following parameters (in addition to those
described in Section 14.1.4: Dening Reactions):
Diusion-Limited Species When there is more than one gaseous reactant taking
part in the particle surface reaction, the diusion-limited species is the species
for which the concentration gradient between the bulk and the particle surface
is the largest. See Figure 14.3.1 for an illustration of this concept. In most
cases, there is a single gas phase reactant and the diusion-limited species
does not need to be dened.
Catalyst Species This option is available only when there are no solid species
dened in the stoichiometry of the particle surface reaction. In such a case,
you will need to specify the solid species that acts as a catalyst for the reaction.
The reaction will proceed only on the particles that contain this solid species.
See Section 14.3.3: Using the Multiple Surface Reactions Model for Discrete-
Phase Particle Combustion for details on dening the particle surface species
mass fractions.
Diusion Rate Constant (C
1,r
in Equation 14.3-6)
Eectiveness Factor (
r
in Equation 14.3-4)
14.3.3 Using the Multiple Surface Reactions Model for Discrete-Phase Particle
Combustion
When you use the multiple surface reactions model, the procedure for setting up a prob-
lem involving a discrete phase is slightly dierent from that outlined in Section 22.11: Steps
for Using the Discrete Phase Models. The revised procedure is as follows:
1. Enable any of the discrete phase modeling options, if relevant, as described in
Section 22.11.5: Physical Models for the Discrete Phase Model.
2. Specify the initial conditions, as described in Section 22.12: Setting Initial Condi-
tions for the Discrete Phase.
3. Dene the boundary conditions, as described in Section 22.13: Setting Boundary
Conditions for the Discrete Phase.
4. Dene the material properties, as described in Section 22.14: Setting Material Prop-
erties for the Discrete Phase.
i
You must select multiple-surface-reactions in the Combustion Model drop-
down list in the Materials panel before you can proceed to the next step.
5. If you have dened more than one particle surface species, for example, carbon
(C<s>) and sulfur (S<s>), you will need to return to the Set Injection Properties
panel (or Set Multiple Injection Properties panel) to specify the mass fraction of each
particle surface species in the combusting particle. Click the Multiple Reactions tab,
and enter the Species Mass Fractions. These mass fractions refer to the combustible
fraction of the combusting particle, and should sum to 1. If there is only one surface
species in the mixture material, the mass fraction of that species will be set to 1,
and you will not specify anything under Multiple Surface Reactions.
6. Set the solution parameters and solve the problem, as described in Section 22.15: So-
lution Strategies for the Discrete Phase.
7. Examine the results, as described in Section 22.16: Postprocessing for the Discrete
Phase.
i
Unsteady particle tracking cannot be performed when the multiple surface
reactions model is used.
14.4 Species Transport Without Reactions
14.4 Species Transport Without Reactions
In addition to the volumetric and surface reactions described in the previous sections, you
can also use FLUENT to solve a species mixing problem without reactions. The species
transport equations that FLUENT will solve are described in Section 14.1.1: Theory, and
the procedure you will follow to set up the non-reacting species transport problem is the
same as that described in Sections 14.1.214.1.6, with some simplications.
The basic steps are listed below:
1. Enable Species Transport in the Species Model panel and select the appropriate
Mixture Material.
See Section 14.1.2: Overview of User Inputs for Modeling Species Transport and
Reactions for information about the mixture material concept, and Section 14.1.3: En-
abling Species Transport and Reactions and Choosing the Mixture Material for
more details about using the Species Model panel.
2. (optional) If you want to model full multicomponent diusion or thermal diusion,
turn on the Full Multicomponent Diusion or Thermal Diusion option.
3. Check and/or dene the properties of the mixture and its constituent species.
Dene Materials...
Mixture properties include the following:
See Section 14.1.4: Dening Properties for the Mixture and Its Constituent Species
for details.
4. Set species boundary conditions, as described in Section 14.1.5: Dening Boundary
Conditions for Species.
No special solution procedures are usually required for a non-reacting species transport
calculation. Upon completion of the calculation, you can display or report the following
quantities:
Mass fraction of species-n
Mole fraction of species-n
Concentration of species-n
Lam Di Coef of species-n
E Di Coef of species-n
Enthalpy of species-n (pressure-based solver calculations only)
Relative Humidity
Mean Molecular Weight
These variables are contained in the Species... and Properties... categories of the variable
selection drop-down list that appears in postprocessing panels. See Chapter 30: Field
Function Denitions for a complete list of ow variables, eld functions, and their def-
initions. Chapters 28 and 29 explain how to generate graphics displays and reports of
data.

Modeling Species Transport and Finite-Rate Chemistry

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Modeling Species Transport and Finite-Rate Chemistry

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Chapter 14.

Modeling Species Transport and Finite-Rate

= volume fraction constant = 2.1377

is a time scale constant equal to 0.4082.

, governed by the Arrhenius rates of Equation 14.1-8,

in Equation 14.1-29 and C

are the temperatures in Equation 22.9-86.

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