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Transport and Adsorption

Introduction
This example demonstrates how you can model phenomena defined in different
dimensions (2D and 1D in this example) in a fully coupled manner using COMSOL
Multiphysics.

In this particular case, the model involves a small parallel-plate reactor with a catalytic
surface. Similar applications where surface processes are of critical importance include
biochip devices and a semiconductor components.

When modeling chemical reactions the reaction rates are commonly functions of the
concentrations of the reactants in the phase that transports the chemicals. However,
for surface reactions it is also necessary to account for the surface concentrations of the
active sites and surface adsorbed species. The mass balances in the bulk of the reactor
must therefore be coupled to the mass balances for species, present only at the surface
of the device.

Model Definition
The first approximation you can make is to reduce the 3D geometry to 2D, which is
reasonable if the variations in concentration are small along the depth of the domain.
Figure 1 shows how the 2D model domain is related to the full 3D reactor geometry.

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3D 2D

Gas outlet

Active surface

Active surface
As

Gas inlet
Modeled cross-section plane

Figure 1: The modeled domain is a parallel plate reactor with an active surface where you
want to model the concentration of surface species. A denotes molecular species dissolved in
gas and As the same species adsorbed on the surface.

MODEL EQUATIONS
The adsorption/desorption reaction at the surface is described by

kf
A AS
kr

where kf and kr are forward and reverse rate constants. A and As are the molecular
species in the gas and adsorbed on active sites on the surface, respectively.

Let θ be the fraction of active sites occupied by adsorbed molecules. The fraction of
free sites is then 1 − θ. Langmuir derived that the rate of desorption of molecules, rdes
(mol/(m2·s)), is proportional to θ and equal to krθ where kr is a constant at constant
temperature. Furthermore, the rate of adsorption of molecules is proportional to both
the fraction of free surface sites, 1 − θ, and to the rate of which molecules strike the
surface. The collision rate is in turn directly proportional the partial pressure of the
species, pA (Pa). The rate of adsorption in mol/(m2·s) is thus rads = kfpA(1 − θ),
where kf is a constant at constant temperature.

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To set up transport and reaction equations in terms of c (bulk gas concentration of A

in mol/m3) and cs (surface concentration of A in mol/m2), make the following
substitutions:

cs
θ = ------
Γs
p A = cRT

where

• Γs is the total surface concentration of active sites (mol/m2)

• R is the gas constant (J/(mol·K))
• T is temperature (K)

which yields

r des = k des c s (1)

and

r ads = k ads c ( Γ s – c s ) (2)

where

• kdes = kr/Γs is the rate constant for the desorption reaction (m3/(mol·s))
• kads = kfRT/Γs is the rate constant for the adsorption reaction (1/s)

Note: The surface concentration is in moles per unit surface.

The material balance for the surface, including surface diffusion and the reaction rate
expression for the formation of the adsorbed species, cs, is:

∂c s
-------- + ∇ ⋅ ( – D s ∇c s ) = r ads – r des
∂t

where Ds represents surface diffusivity. This gives the following equation for the
transport and reaction on the surface:

∂c s
-------- + ∇ ⋅ ( – D s ∇c s ) = k ads c ( Γ s – c s ) – k des c s (3)
∂t

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Equation 3 defines the units of the rate constants kads and kdes. The initial condition
is that the concentration of adsorbed species is zero at the beginning of the process:

cs = 0

The equation for the surface-reaction expression includes the concentration of the
bulk species, c, at the position of the catalyst surface. Thus you must solve the equation
for the surface reaction in combination with the mass balance in the bulk. The coupling
between the mass balance in the bulk and the surface is obtained as a boundary
condition in the bulk’s mass balance. This condition sets the flux of c at the boundary
equal to the rate of the surface reaction and is presented below. The transport in the
bulk of the reactor is described by a convection-diffusion equation:

∂----c-
+ ∇ ⋅ ( – D ∇c + cu ) = 0 (4)
∂t

The initial condition sets the concentration in the bulk at t = 0:

c = c0

In the above equation, D denotes the diffusivity of the reacting species, c is its
concentration, and u is the velocity. In this case, the velocity in the x direction equals
0 while the velocity in the y direction comes from the analytical expression for fully
developed laminar flow between two parallel plates:

( x – 0.5δ ) 2
u = (0,v max 1 – ⎛⎝ -------------------------⎞⎠ )
0.5δ

Here, δ is the distance between the plates, vmax is the maximum local velocity, and
x = 0 at the left boundary of the 2D model geometry depicted on the right in Figure 1.

BOUNDARY CONDITIONS
The boundary conditions for the surface species are insulating conditions according to:

n ⋅ ( – D s ∇c s ) = 0 (5)

For the bulk, the boundary condition at the active surface couples the rate of the
reaction at the surface with the flux of the reacting species and the concentration of
the adsorbed species and bulk species:

n ⋅ ( – D ∇c + cu ) = – k ads c ( Γ s – c s ) + k des c s (6)

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The other boundary conditions for the bulk problem are:

• Inlet: c = c0
• Outlet: n · (−D∇c + cu) = n · cu
• Insulation: n · (−D∇c + cu) = 0

Notes About the COMSOL Implementation

This model deals with a phenomenon (convection-diffusion) occurring in a 2D
domain coupled to another phenomenon (diffusion-reaction) occurring only on a part
of this domain’s 1D boundary. Model the 2D equation (Equation 4) using a Transport
of Diluted Species interface and the 1D equation (Equation 3) with a General Form
Boundary PDE interface on the active-surface boundary. The two interfaces are
coupled through the surface reaction rate expression on the right-hand side of
Equation 3, which becomes a flux in the boundary condition Equation 6 for
Equation 4. The Neumann condition Equation 5 is a natural boundary condition,
which means that you do not need to impose it explicitly.

Results and Discussion

The plot in Figure 2 shows the concentration, c, of the reacting species in the 2D
domain after 2 seconds of operation. The reaction is very fast and has almost reached
steady state in that time frame. Figure 3, which displays the concentration along a
vertical cross section of the active surface, shows that the concentration distribution
exhibits edge effects at both ends of the catalyst. The higher concentration near y = 0
is easy to explain because this is the position closest to the inlet, and this end is
therefore continuously supplied with fresh reactant. The increase in concentration at
the end closer to the outlet is due to diffusion; the edge of the surface can receive
diffusion in all directions within a 90° angle without having to compete for the reactant
supply with other parts of the catalysts. This effect also appears at the edge close to the
inlet.

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Figure 2: Concentration of the reacting species, c, after 2 seconds of operation (t = 2 s).

Figure 3: Concentration of the reacting species along the active surface at t = 2 s.

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The concentration of adsorbed species, cs, shows a similar spatial distribution.

However, while the concentration of the reactant decreases with time, the
concentration of adsorbed species increases. You can also see that the slight spatial
diffusion evens out the concentration gradients somewhat; see Figure 4.

Increasing time

Figure 4: The concentration of adsorbed species increases with time. The edge effect appears
at both edges due to the increased supply of reactants. This figure displays the concentration
after 0.05, 0.5, 1.0, 1.5, and 2.0 s.

The concentration of gas phase species at the surface decreases while the surface
concentration of the adsorbed species increases with time. This implies that the
adsorption rate decreases with time. You can see this effect in Figure 5, which also
shows that after 0.5 s the reaction rate almost reaches steady-state. The upper curve

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shows the reaction rate after 0.05 s, while the lower curve represents the curves for 0.5,
1.0, 1.5, and 2.0 s, which are all on top of each other.

Increasing time

Figure 5: Surface reaction rate at the active surface. The largest reaction rate is obtained
initially and is at the edges of the active surface. The reaction process almost reaches steady
state at 0.5 s.

Model Library path:

COMSOL_Multiphysics/Chemical_Engineering/transport_and_adsorption

Modeling Instructions

MODEL WIZARD
1 Go to the Model Wizard window.
2 Click the 2D button.
3 Click Next.
4 In the Add physics tree, select Chemical Species Transport>Transport of Diluted Species
(chds).

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5 Click Add Selected.

6 In the Add physics tree, select Mathematics>PDE Interfaces>Lower Dimensions>General
Form Boundary PDE (gb).
7 Click Add Selected.
8 In the Dependent variables table, enter the following settings:

cs

9 Click Next.
10 Find the Studies subsection. In the tree, select Preset Studies for Selected
Physics>Time Dependent.
11 Click Finish.

GLOBAL DEFINITIONS
A set of model parameters are available in a text file.

Parameters
1 In the Model Builder window, right-click Global Definitions and choose Parameters.
2 In the Parameters settings window, locate the Parameters section.
3 Click Load from File.
4 Browse to the model’s Model Library folder and double-click the file
transport_and_adsorption_parameters.txt.

GEOMETRY 1
1 In the Model Builder window, under Model 1 click Geometry 1.
2 In the Geometry settings window, locate the Units section.
3 From the Length unit list, choose mm.

Rectangle 1
1 Right-click Model 1>Geometry 1 and choose Rectangle.
2 In the Rectangle settings window, locate the Size section.
3 In the Width edit field, type 0.1.
4 In the Height edit field, type 0.3.
5 Locate the Position section. In the y edit field, type -0.1.
6 Click the Build All button.

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Point 1
1 In the Model Builder window, right-click Geometry 1 and choose Point.
2 In the Point settings window, locate the Point section.
3 In the x edit field, type 0.1.
4 Click the Build All button.

Point 2
1 In the Model Builder window, right-click Geometry 1 and choose Point.
2 In the Point settings window, locate the Point section.
3 In the x edit field, type 0.1.
4 In the y edit field, type 0.1.
5 Click the Build All button.
6 Click the Zoom Extents button on the Graphics toolbar.

DEFINITIONS

Variables 1
1 In the Model Builder window, under Model 1 right-click Definitions and choose
Variables.
2 In the Variables settings window, locate the Geometric Entity Selection section.
3 From the Geometric entity level list, choose Boundary.
4 Select Boundary 5 only.
5 In the Variables settings window, locate the Variables section.
6 In the table, enter the following settings:

NAME EXPRESSION DESCRIPTION

R k_ads*c*(Gamma_s-cs)-k_des*cs Surface reaction rate

Variables 2
1 In the Model Builder window, right-click Definitions and choose Variables.
2 In the Variables settings window, locate the Geometric Entity Selection section.
3 From the Geometric entity level list, choose Domain.
4 Select Domain 1 only.

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5 Locate the Variables section. In the table, enter the following settings:

NAME EXPRESSION DESCRIPTION

v_lam v_max*(1-((x-0.5*delta)/ Inlet velocity profile

(0.5*delta))^2)

TR A N S P O R T O F D I L U T E D S P E C I E S

Convection and Diffusion 1

1 In the Model Builder window, under Model 1>Transport of Diluted Species click
Convection and Diffusion 1.
2 In the Convection and Diffusion settings window, locate the Diffusion section.
3 In the Dc edit field, type D.
4 Locate the Model Inputs section. Specify the u vector as

0 x
v_lam y

Initial Values 1
1 In the Model Builder window, under Model 1>Transport of Diluted Species click Initial
Values 1.
2 In the Initial Values settings window, locate the Initial Values section.
3 In the c edit field, type c0.

Reactions 1
1 In the Model Builder window, right-click Transport of Diluted Species and choose the
domain setting Reactions.
2 Select Domain 1 only.

Concentration 1
1 In the Model Builder window, right-click Transport of Diluted Species and choose the
boundary condition Concentration.
2 Select Boundary 2 only.
3 In the Concentration settings window, locate the Concentration section.
4 Select the Species c check box.
5 In the c0,c edit field, type c0.

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Flux 1
1 In the Model Builder window, right-click Transport of Diluted Species and choose the
boundary condition Flux.
2 Select Boundary 5 only.
3 In the Flux settings window, locate the Inward Flux section.
4 Select the Species c check box.
5 In the N0,c edit field, type -R.

Outflow 1
1 In the Model Builder window, right-click Transport of Diluted Species and choose the
boundary condition Outflow.
2 Select Boundary 3 only.

Symmetry 1
1 In the Model Builder window, right-click Transport of Diluted Species and choose the
boundary condition Symmetry.
2 Select Boundaries 1, 4, and 6 only.

Next, set up the equation and boundary conditions for the surface concentration, cs.

GENERAL FORM BOUNDARY PDE

1 In the Model Builder window, under Model 1 click General Form Boundary PDE.
2 In the General Form Boundary PDE settings window, locate the Boundary Selection
section.
3 From the Selection list, choose Manual.
4 Click Clear Selection.
5 Select Boundary 5 only.
6 Locate the Units section. Find the Dependent variable quantity subsection. From the
list, choose None.
7 In the Unit edit field, type mol/m^2.
8 Find the Source term quantity subsection. In the Unit edit field, type mol/(m^2*s).

General Form PDE 1

1 In the Model Builder window, under Model 1>General Form Boundary PDE click
General Form PDE 1.

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2 In the General Form PDE settings window, click to expand the Equation section.
Comparing this equation with Equation 3 in the Model Definition section leads to
the following settings:
3 Locate the Conservative Flux section. Specify the Γ vector as

-csTx*Ds x
-csTy*Ds y

Here, csTx and csTy refer to the components of the gradient ∇cs restricted to the
plane tangential to the boundary where the interface is defined, that is, Boundary
5. Because this boundary is parallel to the y-axis, only csTy is nonzero in this case.
4 Locate the Source Term section. In the f edit field, type R.

Initial Values 1
The default initial value, 0, for the surface concentration applies for this model, so you
do not need to set it explicitly.

MESH 1

Free Triangular 1
In the Model Builder window, under Model 1 right-click Mesh 1 and choose Free
Triangular.

Size 1
1 In the Model Builder window, under Model 1>Mesh 1 right-click Free Triangular 1 and
choose Size.
2 In the Size settings window, locate the Geometric Entity Selection section.
3 From the Geometric entity level list, choose Boundary.
4 Select Boundary 5 only.
5 Locate the Element Size section. Click the Custom button.
6 Locate the Element Size Parameters section. Select the Maximum element size check
box.
7 In the associated edit field, type 1.5[um].

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8 Click the Build All button.

STUDY 1

Step 1: Time Dependent

1 In the Model Builder window, expand the Study 1 node, then click Step 1: Time
Dependent.
2 In the Time Dependent settings window, locate the Study Settings section.
3 In the Times edit field, type range(0,0.05,2).
4 In the Model Builder window, right-click Study 1 and choose Compute.

RESULTS

Concentration (chds)
1 Click the Zoom Extents button on the Graphics toolbar.
The first default plot shows the concentration of the reacting species at the end of the
simulation interval, t = 2 s.

Next, create a plot of the final concentration at the reacting surface.

1D Plot Group 3
1 In the Model Builder window, right-click Results and choose 1D Plot Group.
2 In the 1D Plot Group settings window, locate the Data section.

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3 From the Time selection list, choose From list.

4 In the Times list, select 2.
5 Right-click Results>1D Plot Group 3 and choose Line Graph.
6 Select Boundary 5 only.
7 In the Line Graph settings window, click Replace Expression in the upper-right corner
of the x-Axis Data section. From the menu, choose Geometry and
Mesh>Coordinate>y-coordinate (y).
8 Locate the x-Axis Data section. From the Unit list, choose mm.
9 Click the Plot button.
The plot should look like that in Figure 3.

Proceed to reproduce the plot in Figure 4 showing the concentration of adsorbed

species at selected times. You can use the plot group you just created as the starting
point.

1D Plot Group 4
1 In the Model Builder window, right-click 1D Plot Group 3 and choose Duplicate.
2 In the 1D Plot Group settings window, locate the Data section.
3 In the Times list, choose 0.05, 0.5, 1, 1.5, and 2.
4 In the Model Builder window, expand the 1D Plot Group 4 node, then click Line Graph
1.
5 In the Line Graph settings window, click Replace Expression in the upper-right corner
of the y-Axis Data section. From the menu, choose General Form Boundary
PDE>Dependent variable cs (cs).
6 Click the Plot button.

Finally, reproduce the plot in Figure 5 of the surface reaction rate at the same times.
Again, use the previous plot group as the starting point.

1D Plot Group 5
1 In the Model Builder window, right-click 1D Plot Group 4 and choose Duplicate.
2 In the Model Builder window, expand the Results>1D Plot Group 5 node, then click
Line Graph 1.
3 In the Line Graph settings window, click Replace Expression in the upper-right corner
of the y-Axis Data section. From the menu, choose Definitions>Surface reaction rate
(R).
4 Click the Plot button.

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