Transport and Adsorption

SOLVED WITH COMSOL MULTIPHYSICS 3.5a

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Transport and Adsorption

This model demonstrates one of the unique features of COMSOL Multiphysics: the possibility to model phenomena defined in different numbers of dimensions in a fully coupled manner. Whereas in most cases you define the reaction rate expression as a function of the concentrations of the reactants and products, in adsorption reactions it is also necessary to model the surface concentrations of the active sites or surface complex. This implies that the mass balance in the bulk of the reactor must be coupled to the mass balance for species present only at the surface of the device. This device could be a catalyst, a biochip, a semiconductor component, or any process with surface-specific species. In this particular case, the model involves a small parallel-plate reactor with an active surface. It is a simple example of surface diffusion and surface reactions coupled to the transport of species between the reacting surface and the surrounding volume. Processes of this kind are found, for instance, in heterogeneous reactors and biacore chips.

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Model Definition
The geometry of the domain appears in Figure 1.
3D 2D Gas outlet

Active surface Active surface

Modeled cross sectional plane

Gas inlet

Figure 1: The modeled domain is a parallel plate reactor with an active surface where you want to model the concentration of surface species. The first approximation you can make is to reduce the 3D geometry to a 2D approximation, which is reasonable if the variations in concentration are small along the depth of the domain.
DOMAIN EQUATIONS

The reaction at the active surface is given as k ads c + cs k des where c is the bulk concentration (mol/m3) is the surface concentration of active sites (mol/m2) cs is the surface concentration of adsorbed species (mol/m2)

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 kads is the rate constant for the forward reaction (m3/(mols)) kdes is the rate constant for the backward 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 ) = k ads c k des c s t where Ds represents surface diffusivity. However, the concentration of active sites is equal to the difference between the total concentration of active sites and the number of sites occupied by the adsorbed species. This gives the following equation for the reaction rate: c s ------- + ( D s c s ) = k ads c ( 0 c s ) k des c s t (1)

In the above equation, 0 represents the total number of active sites available on the surface of the catalyst. Equation 1 also 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 bulks 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 + c u ) = 0 t The initial condition sets the concentration in the bulk at t = 0: c = c0 (2)

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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 0,5 ) u = (0,vmax 1 ----------------------- 0,5
2

Here, is the distance between the plates, and vmax is the maximum local velocity. We assume that the origin for x is at the left edge of the model depicted in Figure 1.
BOUNDARY CONDITIONS

The boundary conditions for the material balance for the surface species are insulating conditions according to: n ( D s c s ) = 0 (3)

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 + c u ) = k ads c ( 0 c s ) + k des c s The other boundary conditions for the bulk problem are: Inlet: c = c0 Outlet: n ( D c + c u ) = n c u Insulation: n ( D c + c u ) = 0

Modeling in COMSOL Multiphysics

This model deals with a phenomenon occurring in a 2D domain (convectiondiffusion) coupled to another phenomenon occurring only at the 1D boundary of the 2D domain (diffusion-reaction). The COMSOL Multiphysics implementation is straightforward in every step except for the definition of the 1D problem, which requires some mathematical background. You need to use weak-form application modes for modeling PDEs on boundaries, edges, or points. To add the 1D boundary equation in the 2D model, use the Weak Form, Boundary application mode. This enables you to formulate the problem with the weak form instead of with the PDE form. An examination of the spatial diffusion on the boundary shows that only the flux tangential to the surface is defined. Therefore, in the weak-form specification you must

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make use of the special tangential derivative variable . For more information about how to specify equations on the weak form, refer to the chapter Deriving the Weak Form on page 360 in the COMSOL Multiphysics Modeling Guide . You define the two equations using the multiphysics feature of COMSOL Multiphysics. Select the two application modes, corresponding to the 2D and 1D material balances, in the Model Navigator.

Results

Figure 2: The concentration of the reacting species, c, after 2 seconds of operation in the 2D cross section (top) and along the active surface (bottom).

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The upper plot in Figure 2 shows the concentration, c, of the reacting species in the 2D subdomain after 2 seconds of operation. The reaction is very fast and almost reaches steady state in that time frame. The lower plot, displaying 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 radial 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. 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 3).

Increasing time

Figure 3: 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.

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The concentration of reacting species decreases while the surface concentration of the adsorbed species increases with time. This implies that the surface reaction rate decreases with time. You can see this effect in Figure 4, which also shows that after 0.5 s the reaction rate almost reaches steady-state. The upper curve 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 4: 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:

adsorption

COMSOL_Multiphysics/Chemical_Engineering/

Modeling Using the Graphical User Interface

The following pages describe how to solve this problem using the graphical user interface.

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MODE L NAVIGATOR

1 Start COMSOL Multiphysics. 2 In the Model Navigator, click the Multiphysics button and select 2D in the Space dimension list. 3 Highlight the application mode COMSOL Multiphysics>Convection and Diffusion>Convection and Diffusion>Transient analysis. Click the Add button. 4 Select the application mode COMSOL Multiphysics>PDE Modes>Weak Form, Boundary.

Type cs in the Dependent variables edit field. Click the Add button.
5 Click OK.

OPTIONS AND SETTINGS

1 From the Options menu, choose Constants. 2 Define the following constants in the Constants dialog box:
NAME EXPRESSION DESCRIPTION

c0 kads kdes theta0 Ds D

1000[mol/m^3] 1e-6[m^3/(mol*s)] 1e-9[1/s] 1000[mol/m^2] 1e-11[m^2/s] 1e-9[m^2/s]

Initial concentration Forward rate constant Backward rate constant Active site concentration Surface diffusivity Gas diffusivity

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NAME

EXPRESSION

DESCRIPTION

v_max delta

1[mm/s] 0.1[mm]

Maximum velocity Channel width

3 Click OK. 4 Open the Axes/Grid Settings dialog box from the Options menu. Specify the following

settings and click OK.

POSITION X-Y LIMITS

x min x max y min y max

-15e-5 25e-5 -15e-5 25e-5

GEOMETRY MODELING

1 Hold down the shift key and click the Rectangle/Square button on the Draw toolbar.

Enter the values listed below in the corresponding edit fields and click OK.
EDIT FIELD VALUE

Width Height x y

1e-4 3e-4 0 -1e-4

2 Click the Zoom Extents button on the Main toolbar. 3 Click the Point button and click on the coordinate (1e-4, 0) in the drawing area.

Click the Point button again and click on (1e-4, 1e-4).

PHYSICS SETTINGS

Expression Variables
1 On the Options menu, point to Expressions and then click Boundary Expressions. 2 Select Boundary 5 in the Boundary selection list and enter the following expression.
NAME EXPRESSION

react_surf

kads*c*(theta0-cs)-kdes*cs

3 Click OK. 4 On the Options menu, select Expressions and then click Subdomain Expressions.

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5 Select Subdomain 1 in the Subdomain selection list and enter the following

expression.
NAME EXPRESSION

v_lam

v_max*(1-((x-0.5*delta)/(0.5*delta))^2)

6 Click OK.

Boundary Conditions
1 From the Multiphysics menu, select 1 Convection and Diffusion (cd). 2 From the Physics menu, choose Boundary Settings. 3 Enter boundary conditions according to the following table:
SETTINGS BOUNDARIES 1, 4, 6 BOUNDARY 2 BOUNDARY 3 BOUNDARY 5

Type c0 N0
4 Click OK.

Insulation/ Symmetry

Concentration
c0

Convective flux

Flux

-react_surf

Subdomain Settings
1 From the Physics menu, choose Subdomain Settings. 2 Select Subdomain 1 in the Subdomain Settings dialog box. 3 Specify the settings as in the following table:
QUANTITY VALUE/EXPRESSION

ts D (isotropic) R u v

1 D 0 0 v_lam

4 Click the Init tab and type c0 in the Concentration, c edit field (c(t0)). 5 Click OK.

Boundary Conditions
Perform this step to specify the transport equation stated in Equation 1. Do so in the Boundary Settings dialog box because the catalytic surface is a boundary of the 2D geometry.

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1 In the Multiphysics menu, select 2 Weak Form, Boundary (wb). 2 From the Physics menu, choose Boundary Settings. 3 Select the Select by group check box, then click in the Boundary selection list to select

all boundaries (Boundaries 16). Clear the Active in this domain check box.
4 Clear the Select by group check box, then select Boundary 5. Check the Active in this domain check box to enable the weak form application mode only on this boundary. 5 Click the Init tab and then type 0 in the cs(t0) edit field. 6 Click the Weak tab. Make the following specifications:
TERM VALUE/EXPRESSION

weak dweak constr

Ds*(-test(csTx)*csTx-test(csTy)*csTy)+ test(cs)*(react_surf-cst) 0 0

7 Click OK.

By adding T to all the weak variables you get the tangential components discussed in the section Modeling in COMSOL Multiphysics on page 4. The lowercase t indicates the derivative with respect to time.

Point Settings
To enforce the boundary condition in Equation on the surface equation you must open the Point Settings dialog box from the Physics menu and select Points 4 and 5. In this case the default settings are correct, that is, the weak, dweak, and constr edit fields should all contain 0, so just leave them as is.
MESH GENERATION

1 From the Mesh menu, choose Free Mesh Parameters. 2 In the Free Mesh Parameters dialog box, click the Boundary tab and select

Boundary 5 from the list.

3 Type 1.5e-6 in the Maximum element size edit field. 4 Click Remesh, then click OK.
COMPUTING THE SOLUTION

1 Click the Solver Parameters button on the Main toolbar. 2 Select Time dependent in the Solver list. 3 In the Time stepping area, type range(0,0.05,2) in the Times edit field.

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4 Click OK. 5 Click the Solve button on the Main toolbar.

PO S T P RO C E S S I N G A N D V I S U A L I ZAT I O N

To generate the right plot in Figure 2:

1 From the Postprocessing menu, choose Domain Plot Parameters. 2 Go to the General tab and click the Line/Extrusion plot button. Select 2 in the Solutions to use list. Customize the plot with text labels by clicking the Title/Axis

button.
3 Click the Line/Extrusion tab and then select Convection and Diffusion (cd)> Concentration, c from the Predefined quantities list. 4 From the Boundary selection list select Boundary 5. 5 Under x-axis data, click the upper option button. Select y from the adjacent list. 6 Click OK.

To generate Figure 3, repeat the previous operations but with these changes:
1 On the General page, go to the Solutions to use list and hold down the Ctrl key to

select the times 0.05, 0.5, 1.0, 1.5, and 2.0.

2 Click the Line/Extrusion tab and then select Weak Form, Boundary (wb)>cs from the Predefined quantities list.

To generate Figure 4, repeat the previous operations but with this change: On the Line/Extrusion tab, type react_surf in the Expression edit field.

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