Chemical Reaction Engineering

COMSOL Multiphysics Training
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CHEMICAL 1
- Chemical Reaction Engineering
Chemical Reaction
g g
Engineering
Mass, Energy, and Momentum Transport
3
0D, very few unknowns. Fast (seconds). 3D Multiphysics. Detailed.
Idealized reacting systems. Lots of unknowns.
Heavy computations.
Modeling Strategy
Space-independent
d ci
Ri
Parameter estimation
dt
Batch Reactor Semi-Batch Reactor
d u x ci
Ri
dx
CSTR Reactor Plug Flow Reactor
Space-dependent
Space-dependent 3D Porous Catalyst
wci
Dci uci Ri
wt
4
Define Chemical Reaction Formulas in perfectly mixed environme
nt (no change in space*)
1. Just type in the

2. The material balances for chemical reaction form
the species are automaticall ulas
y generated as you type in t
he chemical equations
3. The kinetics are

automatically formulat
ed
according to the law of
mass action. If needed,
you can replace the rat
e law with your own
expressions.
Models for batch, semi-batch,

continuous stirred tank reactors, 4. Automatic units of rate consta
and plug-flow reactors are predefin nts, depending on kinetics expre
ed ssions
*The 1D plug flow reactor has no change in time
Reaction Engineering Interface
5
with CAPE-OPEN(Thermodynaimcs)
Run Simulation for the Perfectly Mixed System

– Parameter Estimation
(with Optimization Module)
6
Transport Interfaces
7
Interactions
Transport Phenomena
Momentum Energy Mass
Temperature(T) Concentration(c)
Velocity(u)
Cp rho
Pressure(p) Q rho
k D R
rho
mu
Convection Convection
Reaction Rate(R), Entalpy(H), Entropy(S), Heat Source(Q),

CHEMKIN Thermal Conductivity(k), Diffusion Coefficient(D),
CAPE-OPEN Density(rho), Heat Capacity(Cp), Viscosity(mu)
Reaction Kinetics
CHEMICAL 2 - Electrochemistry
Batteries &
Electrochemistry
Fuel Cells
ࢷ̛୘ଝଥ۱ ࢷएٗߞ
ଥ۱
Electrodeposition Corrosion
osion
ऎ९ଥ۱ ٕ‫ݥ‬ଥ۱
8
The Electrochemistry Interfaces
• Current Distribution Interfaces
– Generic Electrochemical Cell Modeling
– Nernst-Planck Equations
– Flat or porous electrodes Θ&ŽŶůǇї
– Arbitrary number of reactions

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• Electroanalysis ůĞĐƚƌŽĚĞƉŽƐŝƚŝŽŶŽŶůǇї
• Battery Interfaces (B&FC only)

• Corrosion Interfaces (Corrosion Module only)
• Electrodeposition Interfaces (Electrodeposition only)
Electrochemical Reactions
Settings windows for
electrode reactions
for secondary current
• User-Defined distribution
• Bulter-Volmer
• Linearized Bulter-Volmer
• Anodic Tafel equation
• Cathodic Tafel equation
• Concentration
dependent kinetics
9
Electrodeposition & Corrosion – Deformed
Geometry
With Moving Geometry
Without Moving Geometry
10
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11
Thermal Decomposition in a
Parallel Plate Reactor
Introductions
outlet
R OH
Heated cylinder R OH
R
O O
R
Inlet
• Chemical Engineering Module

– Fully coupled momentum, energy and mass
transport
– Strategies for Multiphysics modeling
12
Coupled Three phenomena
Navier-Stokes Equations
velocity
Convection and Diffusion, Reaction
Density,viscosity reaction rate =f(c)

Thermal conductivity (ⵐ㜨 ❄⏈ 䢕㜨)
Heat capacity
Reaction rate
Temperature
Convection and Conduction
⯜⒬⫵ 1 – One-way coupled

• The momentum transport is independent of the energy and
mass transport
• The energy transport depends only on the momentum
transport
• The mass transport depends on both the momentum
transport and the energy transport
• The heat of reaction, Q, is neglected
momentum Heat
Mass
13
Momentum : Navier-stokes equations
wu
U
wt
T

K u u U u u p F
u
0
Energy : Convection and Conduction
wT
U CP kT Q U C P u T T
wt
Mass : Convection and Diffusion § E ·

Ri A exp¨ ¸c
¨R T¸ i
© g ¹
wci
Di ci Ri u ci Ci
wt
⯜⒬⫵ 2 – Fully Coupled

• The momentum transport depends on the energy transport
• The energy transport depends on both momentum and mass
transport
• The mass transport depends on both the momentum transport
and the energy transport
momentum Heat
Mass
14
Momentum : Navier-stokes equations
wu
U
wt
T

K u u U u u p F
u
0
Energy : Convection and Conduction
wT
U CP kT Q U C P u T T
wt
Mass : Convection and Diffusion § E ·

Ri A exp¨ ¸c
¨R T¸ i
© g ¹
wci
Di ci Ri u ci Ci
wt
㫴ⵤ㐑㉘㥉 Model Navigator

(Momentum / Heat / Mass Transport)
Ạ㦤㷨⬀☘ὤ CAD
(2D)
Ɒ㉥ᵆ/᷸ᷱᵆ ㉘㥉 'omain / Boundary Settings

(Momentum / Heat / Mass Transport)
⮈㐐 Mesh
᷸㇤ Solver
䟸㷌⫠ Postprocessing
15
Coupled Three phenomena
Navier-Stokes Equations
velocity
Convection and Diffusion, Reaction
Density,viscosity reaction rate =f(c)

Thermal conductivity (ⵐ㜨 ❄⏈ 䢕㜨)
Heat capacity
Reaction rate
Temperature
Convection and Conduction
Results - velocity
< Constants > < THPS dependent >
16
Results - Temperature
Results - Concentration
17
Solved with COMSOL Multiphysics 5.1
Thermal Decomposition
Introduction
In this tutorial, the heat and mass transport equations are coupled to laminar flow in
order to model exothermic reactions in a parallel plate reactor. It exemplifies how you
can use COMSOL Multiphysics to systematically set up and solve increasingly
sophisticated models using predefined physics interfaces.
Model Definition
In this model you investigate the unimolecular decomposition of a chemical passing
through a parallel plate reactor. A heat–sensitive compound is present in a water
solution. After entering the reactor, the liquid first experiences expansion – due to a
step in the bottom plate. Before exiting, the fluid also passes a heated cylinder.
The full 3D representation of the reactor geometry is given in Figure 1.
Top plate
Outlet
Heated
cylinder
Inlet
Bottom plate
Figure 1: 3D geometry of a parallel plate reactor. The reacting fluid is heated as it passes
the cylinder.
The short inlet section of the reactor is considerably wider than it is high. With such a
geometry, it is reasonable to assume that the laminar flow develops a parabolic velocity
profile between the top and bottom plate. At the same time, the velocity between the
side walls is expected to be close to constant (Ref. 1). As a consequence, you can
reduce the modeling domain to 2D without dramatically reducing the validity of the
1 | THERMAL DECOMPOSITION
18
simulation (see Figure 2).

Top plate
Inlet Heating cylinder Outlet
Bottom plate
Figure 2: Neglecting edge effects, the modeling geometry can be reduced to 2D.
CHEMISTRY
A heat–sensitive chemical (A) undergoes thermal decomposition into fragments (F)
according to the following unimolecular reaction:
k
A F
The reaction rate (SI unit: mol/(m3·s)) is given by:
rate = kc A
where rate constant k (SI unit: s−1) is temperature–dependent according to the

Arrhenius equation:
§ E ·
-----------¸
k = A exp ¨ – R (1)
© g T¹
In Equation 1, A is the frequency factor (1 × 1010 1/s), E the activation energy

(72 × 103 J/mol), Rg the gas constant (8.314 J/(mol·K)), and T the temperature
(SI unit: K).
In addition, the decomposition reaction is exothermic, and the rate of energy expelled
is given by:
Q = – rate ⋅ H
where H is the heat of reaction (−100 kJ/mol).
The conversion of species A in the reactor is a function of the residence time; that is,
it depends on the detailed fluid flow. Furthermore, the decomposition is influenced by
the temperature distribution. A coupled system of transport equations thus describes
the reactor.
19
M O M E N T U M TR A N S P O R T
The Navier-Stokes equations, which govern momentum transport and are solved by
default in the single-phase flow interfaces, give the compressible formulation of the
continuity:
∂ρ
------ + ∇ ⋅ ( ρu ) = 0 (2)
∂t
and the momentum equations:
∂u 2
ρ ------- + ρ u ⋅ ∇u = – ∇p + ∇ ⋅ §© μ ( ∇u + ( ∇u ) T ) – --- μ ( ∇ ⋅ u )I·¹ + F (3)
∂t 3
Here, μ denotes the dynamic viscosity (SI unit: Ns/m2), u the velocity (SI unit: m/
s), ρ the density of the fluid (SI unit: kg/m3), p the pressure (SI unit: Pa), and F a
body force term (SI unit: N/m3). This particular model contains the solution to a
steady-state problem, so the first term in each of the equations above disappears.
Equation 2 governs the flow of a Newtonian fluid in the laminar flow regime. The flow
type in this specific model is determined in The Flow Regime.
Apart from the domain equations you also need to select proper boundary conditions.
At the inlet you specify a velocity vector normal to the boundary:
u ⋅ n = u0 (4)
At the outlet boundary you specify a pressure p = p 0 . Finally, at the surfaces of the
reactor plates and the heating cylinder you set the velocity to zero, that is, a no slip
boundary condition:
u = 0 (5)
By selecting the Laminar Flow interface you can easily associate the momentum
balance (Equation 2) and boundary conditions (Equation 4, Equation 5, and
Equation 5) with your modeling geometry.
E N E R G Y TR A N S P O R T
The energy balance equation applied to the reactor domain considers heat transfer
through convection and conduction:
∇ ⋅ ( – k ∇T ) + ρC p ( u ⋅ ∇ )T = Q (6)
20
In Equation 6, Cp denotes the specific heat capacity (SI unit: J/(kg·K)), k is the
thermal conductivity (SI unit: W/(m·K)), and Q is a sink or source term (SI unit: W/
m3).
At the inlet and at the surface of the heating cylinder you set a Temperature boundary
condition:
T = T0 (7)
T = T cyl (8)
At the outlet you set an Outflow boundary condition. This prescribes that all energy
passing through this boundary does so by means of convective transport. Equivalently,
this means that the heat flux due to conduction across the boundary is zero:
q cond ⋅ n = – k ∇T ⋅ n = 0 (9)
so that the resulting equation for the total heat flux becomes:
q ⋅ n = ρC p T u ⋅ n (10)
This is a useful boundary condition, particularly in convection-dominated energy

balances where the outlet temperature is unknown.
Finally, assume that no energy is transported across the reactor plates, that is, apply a
Thermal Insulation boundary condition:
q⋅n = 0 (11)
Using the Heat Transfer in Fluids interface, you can associate the energy balance
(Equation 6) and boundary conditions (Equation 7 to Equation 11) with the
modeling geometry.
M A S S TR A N S P O R T
The mass transfer in the reactor domain is given by the stationary convection and
diffusion equation:
∇ ⋅ ( – D i ∇c i ) + u ⋅ ∇c i = R i (12)
where Di denotes its diffusion coefficient (SI unit: m2/s), and Ri denotes the reaction
term (SI unit: mol/(m3·s)).
Equation 12 assumes that the species i is diluted in a solvent.
21
For the boundary conditions, specify the concentration of compound A at the inlet:
c i = c i, 0 (13)
At the outlet, specify that the mass flow through the boundary is dominated by
convection. This assumes that any mass flux due to diffusion across this boundary is
zero:
n ⋅ ( – D i ∇c i ) = 0 (14)
and that:
Ni ⋅ n = ci u ⋅ n (15)
Finally, at the surfaces of the reactor plates and the heating cylinder, assume that no
mass is transported across the boundaries—that is, an insulation boundary condition:
Ni ⋅ n = 0 (16)
By selecting the Transport in Diluted Species interface you can easily associate the mass
balance (Equation 12) and boundary conditions (Equation 13 to Equation 16) with
the modeling geometry.
PREPARING FOR MODELING

Before you can start modeling you need to gather the physical data that characterize
your reacting flow. For instance, flow modeling requires you to supply the fluid density
and viscosity. Mass transport requires knowledge of diffusivities and the reaction
kinetics.
Another part of the preparations involves selecting the appropriate physics interfaces
and investigating the couplings between different transport equations.
Transport Properties
The term transport properties refers to the physical properties occurring in the
transport equations (see the previous section). The momentum and heat transfer
equations (Equation 2 and Equation 6) require fluid-specific transport properties:
• Viscosity (η)
• Density (ρ)
• Thermal conductivity (k)
• Heat capacity (Cp)
22
The mass transport equation (Equation 12) requires the following species-specific
property:
• Diffusivities (Di)
You need to supply appropriate values of the transport properties to the physics
interfaces in order to ensure accurate simulation results. In the present example, water
with the dissolved compound A enters the reactor at 300 K. Because water is the
solvent, you can assume that its physical properties are representative for the entire
fluid. The warmest part of the reactor is held at 325 K. Table 1 lists the transport
properties of water as well as the diffusivity of A in water at 300 K and 325 K.
TABLE 1: PHYSICAL PROPERTIES OF LIQUID WATER
PROPERTY AT 300 K AT 325 K
Density (kg/m3) 997 987

Viscosity (Ns/m2) 8.5·10-4 5.3·10-4
Thermal conductivity (W/(m·K)) 0.62 0.66
Heat capacity (J/(kg·K)) 4180 4182
Diffusivity (m2/s) 2.0·10-9 2.0·10-9
When you build this model you make use of the built-in material databases of
COMSOL Multiphysics, which automatically provides temperature-dependent
properties.
The Flow Regime

The Reynolds number indicates whether a flow is in the laminar or turbulent regime:
ρud
Re = -----------
η
As a rule of thumb, a Reynolds number between of 2000 and 2500 marks the
transition from stable streamlines to stable turbulent flow. It is always good practice to
evaluate the Reynolds number related to the specific flow conditions of the model,
because its magnitude guides you to choose the appropriate flow model and
corresponding physics interface.
In the present example, you can evaluate the Reynolds number using values from
Table 1 and setting the velocity to 5 × 10-4 m/s and the characteristic length to
0.007 m:
–4
997 ⋅ 5 ⋅ 10 ⋅ 0.007
Re = -----------------------------------------------------
–4
= 4
8.5 ⋅ 10
23
Calculating the Reynolds number at 325 K produces a nearly identical result.
The Reynolds numbers are well within the limits of the laminar flow regime.
Dilute or Concentrated Mixtures

When modeling mass transport, it is advisable to discriminate between dilute and
concentrated mixtures. For dilute mixtures, Fick’s Law is adequate to describe the
diffusional transport. Furthermore, you can assume that the transport properties of the
fluid are those of the solvent. For concentrated mixtures, on the other hand, other
diffusion models, such as the Maxwell-Stefan model, may be required. The transport
properties of the fluid then depend on the mixture composition.
In COMSOL Multiphysics, the Transport of Diluted Species interface is appropriate

for dilute mixtures, while the Transport of Concentrated Species interface is
recommended for concentrated mixtures.
As a rule of thumb, you can consider concentrations of up to 10 mol% of a solute in a

solvent as a dilute mixture.
In the example at hand, the compound A is dissolved in water at a concentration of

1000 mol/m3. As the concentration of pure water is 55,500 mol/m3, the molar
fraction of A is approximately 2%. Because the mixture is dilute, it is appropriate to
select the Transport of Diluted Species interface for mass transport and to select the
transport properties of water as representative values for the mixture.
Solving Coupled Models

As noted previously, the chemistry occurring in the reactor depends both on the fluid
flow and the temperature distribution in the reactor. More explicitly, the mass
transport equation
∂c i
+ ∇ ⋅ ( – D i ∇c i + c i u ) = R i (17)
∂t
depends on the velocity vector, u, which is solved for in the momentum transfer
equation (Equation 3).
Furthermore, the source term Ri in Equation 17 is a function of the temperature,

which in turn is the dependent variable of the energy transport equation
∂T
ρC p + ∇ ⋅ ( – k ∇T ) + ρC p u ⋅ ∇T = Q
∂t
24
When attempting to solve a coupled system of equations such as the one illustrated
above, it is often a good idea to analyze the couplings involved and then approach the
solution in a stepwise fashion.
In the current model, you first neglect the heat of reaction, Q. This leads to a loose
two-way coupling between the transport equations:
• The momentum transport is weakly dependent on the energy and mass transport
through the material properties.
• The energy transport depends only on the momentum transport.
• The mass transport depends on both the momentum transport and the energy
transport.
This structure suggests that it is possible to solve the problem sequentially in the
following order: First solve the momentum transport and energy transport problem.
Then add the mass transport and investigate the difference.
The last step leads to a fully coupled problem:
• The momentum transport depends on the energy transport.

• The energy transport depends on both momentum and mass transport (added heat
of reaction).
• The mass transport depends on both the momentum transport and the energy
transport.
In this case you must solve the equations describing all transport phenomena
simultaneously.
25
Results and Discussion

Figure 3 shows the velocity field in the reactor domain along with arrows indicating
the velocity magnitude.
Figure 3: Velocity field (m/s) in the reactor.
The cross-sectional area of the fluid increases at the step and decreases at the cylinder,
leading to a corresponding local reduction and then increase in the fluid velocity.
Recirculation zones appear after the step and the cylinder.
26
The water solution enters the reactor at a temperature of 300 K and is heated as it
passes the cylinder (325 K). Figure 4 shows the temperature distribution in the reactor
domain at steady state.
Figure 4: A water solution enters the reactor at 300 K and is heated by a cylinder kept at
325 K.
27
At the reactor inlet, the concentration of A is 1000 mol/m3. Figure 5 shows the
concentration of A as the compound undergoes decomposition.
Figure 5: Concentration of the heat sensitive chemical (A) (mol/m3) as function of

position in the reactor.
These plots make it possible to identify some general trends. It is clear that
decomposition occurs mainly after the liquid has been heated by the cylinder. In the
first half of the reactor, where the temperature is relatively low, decomposition is still
fairly advanced near the wall and after the step. This is due to the longer residence times
in these areas. In the second part of the reactor, where heating takes place, regions with
relatively high concentrations of compound A are visible. This also makes physical
sense because the water velocity is relatively high.
The temperature distribution in the entire reactor is affected by the heat of reaction.
As shown in Figure 6, the maximum fluid temperature now exceeds the temperature
28
of the heating cylinder. Furthermore, the water temperature is higher than 300 K in
the region between the inlet and the cylinder.
Figure 6: Reactor temperature (K) when the heat of reaction is taken into account.
29
Figure 7 plots the rate of reaction as a function of the position in the reactor. Clearly,
significant reaction now occurs in the first part of the reactor, before the heating
cylinder.
Figure 7: Significant decomposition of compound A occurs in the first half of the reactor.
Reference
1. H. Schlichting, Boundary Layer Theory, 4th ed., McGraw Hill, p. 168, 1960.
Application Library path: Chemical_Reaction_Engineering_Module/

Reactors_with_Mass_and_Heat_Transfer/thermal_decomposition
Modeling Instructions
From the File menu, choose New.
NEW
1 In the New window, click Model Wizard.
30
MODEL WIZARD
1 In the Model Wizard window, click 2D.
2 In the Select physics tree, select Fluid Flow>Single-Phase Flow>Laminar Flow (spf).
3 Click Add.
4 Click Study.
5 In the Select study tree, select Preset Studies>Stationary.
6 Click Done.
GLOBAL DEFINITIONS
First define some parameters.
Parameters
1 On the Home toolbar, click Parameters.
2 In the Settings window for Parameters, locate the Parameters section.
3 Click Load from File.
4 Browse to the application’s Application Library folder and double-click the file
thermal_decomposition_parameters.txt.
GEOMETRY 1
Rectangle 1 (r1)
1 On the Geometry toolbar, click Primitives and choose Rectangle.
2 In the Settings window for Rectangle, locate the Size section.
3 In the Width text field, type W1.
4 In the Height text field, type H1.
Rectangle 2 (r2)
3 In the Width text field, type W2.
4 In the Height text field, type H2.
Circle 1 (c1)
1 On the Geometry toolbar, click Primitives and choose Circle.
2 In the Settings window for Circle, locate the Size and Shape section.
3 In the Radius text field, type R1.
31
4 Locate the Position section. In the x text field, type xpos.

5 In the y text field, type ypos.
Difference 1 (dif1)
1 On the Geometry toolbar, click Booleans and Partitions and choose Difference.
2 Select the object r1 only to add it to the Objects to add list.
3 In the Settings window for Difference, locate the Difference section.
4 Find the Objects to subtract subsection. Select the Active toggle button.
5 Select the objects r2 and c1 only.
6 Right-click Component 1 (comp1)>Geometry 1>Difference 1 (dif1) and choose Build
Selected.
ADD MATERIAL
1 On the Home toolbar, click Add Material to open the Add Material window.
2 Go to the Add Material window.
3 In the tree, select Liquids and Gases>Liquids>Water.
4 Click Add to Component in the window toolbar.
5 On the Home toolbar, click Add Material to close the Add Material window.
MATERIALS
Water (mat1)
By default, the first material you add applies on all domains so you can keep the
Geometric Scope settings.
DEFINITIONS
In preparation for defining boundary conditions, it is practical to define some named
selections.
Explicit 1
1 On the Definitions toolbar, click Explicit.
2 In the Model Builder window, under Component 1 (comp1)>Definitions right-click
Explicit 1 and choose Rename.
3 In the Rename Explicit dialog box, type Inlet in the New label text field.
4 Click OK.
5 In the Settings window for Explicit, locate the Input Entities section.
6 From the Geometric entity level list, choose Boundary.
32
7 Select Boundary 1 only.
Explicit 2
3 In the Rename Explicit dialog box, type Outlet in the New label text field.
4 Click OK.
Explicit 3
3 In the Rename Explicit dialog box, type Heater in the New label text field.
4 Click OK.
7 Select Boundaries 7–10 only.
Follow the instructions below to set up the Fluid Flow interface. The fluid
properties are automatically taken from the material assigned to the reactor domain,
so all you need to do is to define inlet and outlet boundary conditions.
LAMINAR FLOW (SPF)
Inlet 1
1 On the Physics toolbar, click Boundaries and choose Inlet.
2 In the Settings window for Inlet, locate the Boundary Selection section.
3 From the Selection list, choose Inlet.
4 Locate the Velocity section. In the U0 text field, type 5e-4.
Outlet 1
1 On the Physics toolbar, click Boundaries and choose Outlet.
2 In the Settings window for Outlet, locate the Boundary Selection section.
33
3 From the Selection list, choose Outlet.

4 Locate the Pressure Conditions section. Select the Normal flow check box.
This concludes the setup of the Laminar Flow interface. In the next step you will
compute the solution. A mesh is created automatically. If you wish, you can inspect
the mesh by clicking the Mesh node.
STUDY 1
1 In the Model Builder window, right-click Study 1 and choose Rename.
2 In the Rename Study dialog box, type Isothermal Flow in the New label text field.
3 Click OK.
4 On the Home toolbar, click Compute.
RESULTS
Velocity (spf)
1 In the Model Builder window, under Results right-click Velocity (spf) and choose
Arrow Surface.
2 On the Velocity (spf) toolbar, click Plot.
3 Click the Zoom Extents button on the Graphics toolbar.
4 In the Model Builder window, right-click Velocity (spf) and choose Rename.
5 In the Rename 2D Plot Group dialog box, type Flow Field in the New label text field.
6 Click OK.
At this point, move on to include a Heat Transfer in Fluids interface and extend the
model to account for a nonisothermal flow situation.
ADD PHYSICS
1 On the Home toolbar, click Add Physics to open the Add Physics window.
2 Go to the Add Physics window.
3 In the Add physics tree, select Heat Transfer>Heat Transfer in Fluids (ht).
4 Find the Physics interfaces in study subsection. In the table, enter the following
settings:
Studies Solve
Isothermal Flow
34
6 On the Home toolbar, click Add Physics to close the Add Physics window.
H E A T TR A N S F E R I N F L U I D S ( H T )
Temperature 1
1 On the Physics toolbar, click Boundaries and choose Temperature.
2 In the Settings window for Temperature, locate the Boundary Selection section.
4 Locate the Temperature section. In the T0 text field, type 300[K].
Temperature 2
1 On the Physics toolbar, click Boundaries and choose Temperature.
2 In the Settings window for Temperature, locate the Boundary Selection section.
3 From the Selection list, choose Heater.
4 Locate the Temperature section. In the T0 text field, type 325[K].
Outflow 1
1 On the Physics toolbar, click Boundaries and choose Outflow.
2 In the Settings window for Outflow, locate the Boundary Selection section.
MULTIPHYSICS
Couple the Laminar Flow interface to the Heat Transfer in Fluids interface, i.e., the
pressure and velocity are inputs taken from the Laminar Flow interface
1 On the Physics toolbar, click Multiphysics and choose Global>Flow Coupling.

Coupling the Heat Transfer in Fluids interface to the Laminar Flow interface, i.e.,
temperature is an input from the Heat Transfer in Fluids interface.
2 On the Physics toolbar, click Multiphysics and choose Global>Temperature Coupling.
ADD STUDY
1 On the Home toolbar, click Add Study to open the Add Study window.
2 Go to the Add Study window.
3 Find the Studies subsection. In the Select study tree, select Preset Studies>Stationary.
4 Click Add Study in the window toolbar.
5 On the Home toolbar, click Add Study to close the Add Study window.
35
STUDY 2
Step 1: Stationary
1 In the Settings window for Stationary, click to expand the Values of dependent
variables section.
2 Locate the Values of Dependent Variables section. Select the Initial values of variables
solved for check box.
3 From the Method list, choose Solution.
4 From the Study list, choose Isothermal Flow, Stationary.
With this selection the solver will take the solution to the isothermal flow case as
starting guess for the flow field and pressure variables.
6 In the Rename Study dialog box, type Non-isothermal Flow in the New label text
field.
7 Click OK.
8 In the Settings window for Study, locate the Study Settings section.
9 Clear the Generate default plots check box.
RESULTS
2D Plot Group 3
1 On the Home toolbar, click Add Plot Group and choose 2D Plot Group.
2 In the Settings window for 2D Plot Group, locate the Data section.
3 From the Data set list, choose Non-isothermal Flow/Solution 2.
4 Right-click Results>2D Plot Group 3 and choose Surface.
5 In the Settings window for Surface, click Replace Expression in the upper-right corner
of the Expression section. From the menu, choose Component 1>Heat Transfer in
Fluids>Temperature>T - Temperature.
6 On the 2D Plot Group 3 toolbar, click Plot.
7 In the Model Builder window, right-click 2D Plot Group 3 and choose Rename.
8 In the Rename 2D Plot Group dialog box, type Temperature in the New label text
field.
9 Click OK.
36

Now move on to extend the model to include mass transport and chemical reaction.
ADD PHYSICS
3 In the Add physics tree, select Chemical Species Transport>Chemistry (chem).
4 Find the Physics interfaces in study subsection. In the table, enter the following
settings:
Studies Solve
Isothermal Flow
Non-isothermal Flow

6 In the Add physics tree, select Chemical Species Transport>Transport of Diluted Species
(tds).
7 Click to expand the Dependent variables section. In the table, enter the following
settings:
Studies Solve
Isothermal Flow
Non-isothermal Flow
8 In the Concentrations table, enter the following settings:
cA

CHEMISTRY (CHEM)
1 In the Model Builder window, under Component 1 (comp1) click Chemistry (chem).
2 In the Settings window for Chemistry, locate the Model Inputs section.
3 From the T list, choose Temperature (ht).
Reaction 1
1 On the Physics toolbar, click Domains and choose Reaction.
37
2 In the Settings window for Reaction, locate the Reaction Formula section.
3 In the Formula text field, type A=>F.
4 Click Apply.
5 Locate the Rate Constants section. Select the Use Arrhenius expressions check box.
6 In the Af text field, type A.
7 In the Ef text field, type E.
8 Locate the Reaction Thermodynamic Properties section. From the Enthalpy of reaction
list, choose User defined.
9 In the H text field, type H.
Species: F
1 In the Model Builder window, under Component 1 (comp1)>Chemistry (chem) click
Species: F.
2 In the Settings window for Species, click to expand the Species concentration/activity
section.
3 Locate the Species Concentration/Activity section. Select the Locked concentration/
activity check box.
TR A N S P O R T O F D I L U T E D S P E C I E S ( T D S )
On the Physics toolbar, click Chemistry (chem) and choose Transport of Diluted Species
(tds).
Transport Properties 1
1 In the Model Builder window, expand the Transport of Diluted Species (tds) node, then
click Transport Properties 1.
2 In the Settings window for Transport Properties, locate the Diffusion section.
3 In the DcA text field, type 2e-9.
Inflow 1
1 On the Physics toolbar, click Boundaries and choose Inflow.
2 In the Settings window for Inflow, locate the Boundary Selection section.
4 Locate the Concentration section. In the c0,cA text field, type 1000.
Outflow 1
38
Reactions 1
1 On the Physics toolbar, click Domains and choose Reactions.
2 Select Domain 1 only.
3 In the Settings window for Reactions, locate the Reaction Rates section.
4 From the RcA list, choose Rate expression for species A (chem).
The chemical reaction generates heat. Take this into account by adding a Heat
Source node to the Heat Transfer in Fluids interface.
H E A T TR A N S F E R I N F L U I D S ( H T )
Heat Source 1
1 On the Physics toolbar, click Domains and choose Heat Source.
3 In the Settings window for Heat Source, locate the Heat Source section.
4 From the Q0 list, choose Heat source of reactions (chem).
MULTIPHYSICS
Couple the Laminar Flow interface to the Transport of Diluted Species interface, i.e.,
the velocity is an input from the Laminar Flow interface.
1 On the Physics toolbar, click Multiphysics and choose Global>Flow Coupling.

2 In the Settings window for Flow Coupling, locate the Flow Coupling section.
3 From the Destination list, choose Transport of Diluted Species (tds).
Couple the Heat Transfer in Fluids interface to the Transport of Diluted Species
interface, i.e., temperature is an input from the Heat Transfer in Fluids interface.
4 On the Physics toolbar, click Multiphysics and choose Global>Temperature Coupling.
5 In the Settings window for Temperature Coupling, locate the Temperature Coupling
section.
6 From the Destination list, choose Transport of Diluted Species (tds).
ADD STUDY
39

STUDY 3
Step 1: Stationary
1 In the Model Builder window, under Study 3 click Step 1: Stationary.
2 In the Settings window for Stationary, click to expand the Values of dependent
variables section.
3 Locate the Values of Dependent Variables section. Select the Initial values of variables
solved for check box.
4 From the Method list, choose Solution.
5 From the Study list, choose Non-isothermal Flow, Stationary.
7 In the Rename Study dialog box, type Fully Coupled in the New label text field.
8 Click OK.
RESULTS
Temperature
2 From the Data set list, choose Fully Coupled/Solution 3.
4 On the Temperature toolbar, click Plot.
Create new plot groups and generate surface plots for the concentration and the
reaction rate.
2D Plot Group 4
40
of the Expression section. From the menu, choose Component 1>Transport of Diluted
Species>cA - Concentration.
9 In the Rename 2D Plot Group dialog box, type Concentration in the New label text
field.
10 Click OK.
2D Plot Group 5
of the Expression section. From the menu, choose Component 1>Transport of Diluted
Species>tds.R_cA - Total rate expression.
9 In the Rename 2D Plot Group dialog box, type Reaction Rate in the New label text
field.
10 Click OK.
41
0QUJNJ[BUJPOPG
B$BUBMZUJD.JDSPSFBDUPS
42
Optimization of a Catalytic
Microreactor
43
44
Optimization of a Catalytic
Micr o r e a c to r
Introduction
In this example model, a solution is pumped through a catalytic bed, where a reactant
undergoes chemical reaction as it gets in contact with the catalyst. The purpose of the
model is to maximize the total reaction rate for a given total pressure difference across
the bed by finding an optimal catalyst distribution. The distribution of the porous
catalyst determines the total reaction rate in the bed. A large amount of catalyst results
in a low flow rate through the bed while less catalyst gives a high flow rate but low
conversion of the reactant.
This modeling example is based on Ref. 1.
Note: This application requires the Optimization Module.
Model Definition
The model geometry is shown in Figure 1. The reactor consists of an inlet channel, a
fixed catalytic bed, and an outlet channel.
1 | OPTIMIZATION OF A CATALYTIC MICROREACTOR

45
Reacting domain
Inlet Outlet
Symmetry boundary
Figure 1: Model geometry.
The optimal catalyst distribution should maximize the average reaction rate, which is
expressed as the integral of the local reaction rate, r (SI unit: mol/(m3·s)), over the
domain, Ω. This is equivalent to minimizing the negative of this average reaction rate:
1 ½
min ® – ------------------- r dΩ ¾
³
¯ vol(Ω ) ¿
Ω
Assuming a first-order catalytic reaction with respect to the reactant species, the local
reaction rate is determined by
r = k a ( 1 – ε )c (1)
where ε denotes the volume fraction of solid catalyst, c refers to the concentration (SI
unit: mol/m3), and ka is the rate constant (SI unit: 1/s).
The mass transport is described by the convection and diffusion equation
∇ ⋅ ( – D∇c ) = r – u ⋅ ∇c
where u denotes the velocity vector (SI unit: m/s) and D is the diffusion coefficient
(SI unit: m2/s). The Navier-Stokes equations describe the fluid flow:
T
ρ ( u ⋅ ∇ )u = – ∇ p + ∇ ⋅ μ ( ∇u + ( ∇u ) ) – α ( ε )u
(2)
∇⋅u = 0

46
The coefficient α(ε) depends on the distribution of the porous catalyst as
μ q(1 – ε)
α ( ε ) = ------------------2- ⋅ -------------------- (3)
Da ⋅ L q+ε
where Da is the Darcy number; L is the length scale (SI unit: m); and q is a
dimensionless parameter, the interpretation of which is discussed in the next section.
From Equation 3, the direct conclusion is that when ε equals 1, α equals zero and
Equation 2 reduces to the ordinary Navier-Stokes equations. In this case the reaction
rate is zero; see Equation 1.
To summarize, the optimization problem is
1 ½
min ® – ------------------ ( k a ( 1 – ε )c ) dΩ ¾
³ (4)
vol(Ω )
ε ¯ Ω
¿
where
T
ρ ( u ⋅ ∇ )u = – ∇ p + ∇ ⋅ μ ( ∇u + ( ∇u ) ) – α ( ε )u
∇⋅u = 0
∇ ⋅ ( – D∇c ) = r – u ⋅ ∇c
0≤ε≤1
and physical boundary conditions apply.
CONVEX OPTIMIZATION PROBLEMS

One of the most important characteristics of an optimization problem is whether or
not the problem is convex. This section therefore briefly describes this property. For a
more general discussion of the subject, see for example Ref. 2.
A set C is said to be convex if for any two members x, y of C, the following relation
holds:
tx + ( 1 – t )y ∈ C for every t ∈ [ 0, 1 ]
that is, the straight line between x and y is fully contained in C. A convex function is a
mapping f from a convex set C such that for every two members x, y of C
f ( tx + ( 1 – t )y ) ≤ t f ( x ) + ( 1 – t )f ( y ) for every t ∈ [ 0, 1 ] (5)

47
An optimization problem is said to be convex if the following conditions are met:
• the design domain is convex

• the objective and constraints are convex functions
The importance of convexity follows simply from the result that if x* is a local
minimum to a convex optimization problem, then x* is also a global minimum. This
is easily proven by simply assuming that there is a y such that f(y) < f(x*), and then
using Equation 5.
This particular optimization problem is nonlinear, because a change in ε implies a

change in the concentration, c. Because of this implicit dependence, it is very difficult
to determine whether or not the objective is convex. There is therefore no guarantee
that the optimal solution you obtain is globally optimal or unique. In the best of cases,
running the optimization gives a good local optimum.
The parameter q can be used to smoothen the interfaces between the catalyst and the
open channel. To see the effect of this parameter, rewrite Equation 3 as
μ 1–ε
α ( ε ) = ------------------2- ⋅ -------------
Da ⋅ L 1 + --ε-
q

48
It follows that when q approaches infinity, α is the (inverse) porosity. On the other
hand, lowering the value of q decreases the magnitude of α.
Figure 2: q(1 − ε)/(q − ε) plotted as a function of ε for different values of q.
Figure 2 shows q(1 − ε)/(q − ε) plotted as a function of ε for different values of q. This
plot shows that lowering the value of q, increases the convexity of the force coefficient.
For a low q value, an increase in ε around 0.5, imposes a small increase of the force
coefficient, while for a higher value of q, a change in ε imposes an almost equal change
for the whole range. Therefore, for a lower q value, the solution is not sharp at the
interfaces. On the other hand, for small values of ε, the force term decreases rapidly
when q is small, and thus affects the flow field to a much wider extent. In the limit
when q approaches infinity, α as a function of ε is a straight line.

Figure 3 shows the velocity field in the empty channel, this is the starting point for the
optimization.

49
Figure 3: Velocity field in the open channel.
Figure 4: Distribution of the porous catalyst seen in black and open channel in white.

50
Figure 4 shows the distribution of the porous catalyst in black and the open channels
in white. This result shows that, optimally, the supply of the reactant should be
distributed over a large area of the reactor. Note also that the amount of open channel
volume is significant.
Figure 5 shows the concentration distribution in the reactor. This plot shows how the
porous catalyst is fed with the reactant through the open channels. The plot naturally
resembles that of Figure 4.
Figure 5: Concentration distribution in the reactor after optimization.
Let
Fi = ³ nflow ⋅ ( – D∇c + cu ) ds
∂Ω i
where nflow refers to the normal to the boundary ∂Ωi in the flow direction (that is,
pointing in to the domain at the inlet and out from the domain at the outlet). Then
Fi is a measurement of the flow of the species with concentration c through the
boundary ∂Ωi per unit length in the transverse dimension. The conversion, X, of the
reactant is defined as

51
F in – F out
X = --------------------------
F in
In this case, the conversion of the reactant is around 50%.
Figure 6 shows the velocity field in the reactor. The porous catalyst slows down the
flow significantly compared to Figure 3.
Figure 6: Velocity field in the reactor after optimization.
References
1. F. Okkels and H. Bruus, “Scaling Behavior of Optimally Structured Catalytic
Microfluidic Reactors,” Phys. Rev. E, vol. 75, pp. 016301 1–4, 2007.
2. S.G. Nash and A. Sofer, Linear and Nonlinear Programming, McGraw-Hill,

1995.
Application Library path: Chemical_Reaction_Engineering_Module/

Reactors_with_Mass_Transfer/microreactor_optimization

52
NEW
MODEL WIZARD
2 In the Select physics tree, select Fluid Flow>Single-Phase Flow>Laminar Flow (spf).
3 Click Add.
4 In the Select physics tree, select Chemical Species Transport>Transport of Diluted
Species (tds).
5 Click Add.
6 In the Select physics tree, select Mathematics>Optimization and
Sensitivity>Optimization (opt).
7 Click Add.
8 Click Study.
9 In the Select study tree, select Preset Studies for Selected Physics Interfaces>Stationary.
10 Click Done.
GLOBAL DEFINITIONS
Parameters
3 In the table, enter the following settings:
Name Expression Value Description

q 0.04 0.04 Optimization parameter
Da 1e-4 1E-4 Darcy number
L 1[mm] 0.001 m Length scale
rho 1000[kg/m^3] 1000 kg/m³ Density of water
eta 1e-3[Pa*s] 0.001 Pa·s Viscosity of water
c_in 1[mol/m^3] 1 mol/m³ Concentration at inlet

53

k_a 0.25[mol/ 0.25 mol/(m³·s) Reaction rate
(m^3*s)] coefficient
delta_p 0.25[Pa] 0.25 Pa Pressure drop
vol 3*L*6*L 1.8E-5 m² Volume of the reacting
domain
D 3e-8[m^2/s] 3E-8 m²/s Diffusion coefficient
GEOMETRY 1
Next, create the geometry. The reactor consists of three domains: the inlet channel,
the reacting domain, and the outlet channel (see Figure 1).
1 In the Model Builder window, under Component 1 (comp1) click Geometry 1.

2 In the Settings window for Geometry, locate the Units section.
3 From the Length unit list, choose mm.
Rectangle 1 (r1)
3 In the Width text field, type 2*L.
4 In the Height text field, type L.
Rectangle 2 (r2)
4 In the Height text field, type 3*L.
5 Locate the Position section. In the x text field, type 2*L.
Rectangle 3 (r3)
4 In the Height text field, type L.
5 Locate the Position section. In the x text field, type 8*L.
6 Right-click Component 1 (comp1)>Geometry 1>Rectangle 3 (r3) and choose Build
Selected.

54

The geometry should now look like that in Figure 1.
DEFINITIONS
Define integration couplings to use for calculating the conversion of the reactant.
Integration 1 (intop1)
1 On the Definitions toolbar, click Component Couplings and choose Integration.
2 In the Settings window for Integration, locate the Source Selection section.
2 In the Settings window for Integration, locate the Source Selection section.
Variables 1
1 On the Definitions toolbar, click Local Variables.
2 In the Settings window for Variables, locate the Variables section.
Name Expression Unit Description

F_in intop1(tds.tflux_cx mol/(m·s) Influx
)
F_out intop2(tds.tflux_cx mol/(m·s) Outflux
)
X (F_in-F_out)/F_in Conversion of reactant
Here, tds.tfluxx_c is the COMSOL Multiphysics variable for the x-component of

the total flux.
Variables 2
1 On the Definitions toolbar, click Local Variables.
2 In the Settings window for Variables, locate the Geometric Entity Selection section.
3 From the Geometric entity level list, choose Domain.

55
5 Locate the Variables section. In the table, enter the following settings:
Name Expression Unit Description

phi k_a*(1-epsilon)*c Local reaction rate
alpha (eta/ Drag-force coefficient
(Da*L^2))*q*(1-epsi
lon)/(q+epsilon)
ADD MATERIAL
3 In the tree, select Built-In>Water, liquid.
LAMINAR FLOW (SPF)
Volume Force 1
1 On the Physics toolbar, click Domains and choose Volume Force.
3 In the Settings window for Volume Force, locate the Volume Force section.
4 Specify the F vector as
-alpha*u x
-alpha*v y
Inlet 1
3 In the Settings window for Inlet, locate the Boundary Condition section.
4 From the list, choose Pressure.
5 Locate the Pressure Conditions section. In the p0 text field, type delta_p.
Symmetry 1
1 On the Physics toolbar, click Boundaries and choose Symmetry.
2 Select Boundaries 2, 5, and 9 only.

56
Outlet 1
1 In the Model Builder window, expand the Component 1 (comp1)>Transport of Diluted
Species (tds) node, then click Transport Properties 1.
2 In the Settings window for Transport Properties, locate the Model Inputs section.
3 From the u list, choose Velocity field (spf).
4 Locate the Diffusion section. In the Dc text field, type D.
Reactions 1
1 On the Physics toolbar, click Domains and choose Reactions.
3 In the Settings window for Reactions, locate the Reaction Rates section.
4 In the Rc text field, type -phi.
Concentration 1
1 On the Physics toolbar, click Boundaries and choose Concentration.
2 In the Settings window for Concentration, locate the Concentration section.
3 Select the Species c check box.
4 In the c0,c text field, type c_in.
Outflow 1
This completes the setup of the physics. Now set up the optimization problem.
OPTIMIZATION (OPT)
Define the control variable epsilon, select its shape, and constrain its values to the
interval [0, 1].
Control Variable Field 1

1 On the Physics toolbar, click Domains and choose Control Variable Field.

57

Because the porous catalyst is only used in the reacting domain you can deactivate
the inlet and outlet channels.
3 In the Settings window for Control Variable Field, locate the Control Variable
section.
4 In the Control variable name text field, type epsilon.
5 In the Initial value text field, type 1.
6 Locate the Discretization section. From the Element order list, choose Linear.
Control Variable Bounds 1

1 In the Model Builder window, right-click Control Variable Field 1 and choose Control
Variable Bounds.
2 In the Settings window for Control Variable Bounds, locate the Bounds section.
3 In the Upper bound text field, type 1.
Next, define the objective function.
Integral Objective 1
1 On the Physics toolbar, click Domains and choose Integral Objective.
3 In the Settings window for Integral Objective, locate the Objective section.
4 In the Objective expression text field, type -phi/vol.
This example requires a fine mesh, both to solve the physics problem and to resolve
the topology optimization problem.
MESH 1
1 In the Model Builder window, under Component 1 (comp1) click Mesh 1.
2 In the Settings window for Mesh, locate the Mesh Settings section.
3 From the Element size list, choose Finer.
4 Click the Build All button.
STUDY 1
Although you can choose to solve the optimization problem directly, it can be useful
to check that the solution for the PDE problem looks sound before starting the
optimization.

58
RESULTS
Velocity (spf)
The first default plot (see Figure 3) shows the velocity field in the reactor.
Now solve the optimization problem.
STUDY 1
Step 1: Stationary
1 In the Model Builder window, expand the Study 1 node, then click Step 1: Stationary.
2 In the Settings window for Stationary, click to expand the Results while solving
section.
3 Locate the Results While Solving section. Select the Plot check box.
This setting gives a plot of the evolving velocity distribution in the Graphics window.
Optimization
1 On the Study toolbar, click Optimization.
Choose the SNOPT solver rather than MMA since the objective function contains
an implicit trade-off between a high flow rate and a high active catalyst area. This
makes the objective severely nonlinear.
2 In the Settings window for Optimization, locate the Optimization Solver section.
3 From the Method list, choose SNOPT.
Solution 1
1 On the Study toolbar, click Show Default Solver.
2 In the Model Builder window, expand the Solution 1 node.
3 In the Model Builder window, expand the Study 1>Solver Configurations>Solution
1>Optimization Solver 1 node, then click Stationary 1.
4 In the Settings window for Stationary, locate the General section.
5 In the Relative tolerance text field, type 1e-6.
6 On the Study toolbar, click Compute.
RESULTS
Velocity (spf)
The velocity field in the reactor after optimization should resemble that in Figure 6.

59
Concentration (tds)
The third default plot shows the concentration distribution in the reactor after
optimization (Figure 5).
To reproduce the plot in Figure 4, modify the default plot with the following steps.
2D Plot Group 4
1 In the Model Builder window, under Results click 2D Plot Group 4.
2 In the Settings window for 2D Plot Group, click to expand the Title section.
3 From the Title type list, choose Manual.
4 In the Title text area, type Distribution of porous catalyst.
5 In the Model Builder window, expand the 2D Plot Group 4 node, then click Surface 1.
of the Expression section. From the menu, choose Component
1>Optimization>epsilon - Control variable epsilon.
7 Locate the Coloring and Style section. From the Color table list, choose GrayScale.
8 Clear the Color legend check box.
11 Right-click Results>2D Plot Group 4>Surface 1 and choose Rename.
12 In the Rename Surface dialog box, type Porous Catalyst in the New label text field.
13 Click OK.
Derived Values
To display the result for the conversion rate, continue as follows:
1 On the Results toolbar, click Global Evaluation.

2 In the Settings window for Global Evaluation, click Replace Expression in the
upper-right corner of the Expression section. From the menu, choose Component
1>Definitions>Variables>X - Conversion of reactant.
3 Click the Evaluate button.
TABLE
1 Go to the Table window.
The value appears in the Table window below the Graphics window.

60
8JSF&MFDUSPEF
61
Wire Electrode
Modeling of Electrochemical Cells

• Primary current distribution
– Accounts only for Ohmic effects in the simulation of current density distribution
and performance of the cell:
• Neglects the influence of concentration variations in the electrolyte
• Neglects the influence of electrode kinetics on the performance of the cell, i.e. activation o
verpotential is neglected (losses due to activation energy)
• Secondary current distribution

– Accounts only for Ohmic effects and the effect of electrode kinetics in the simul
ation of current density distribution and performance of the cell:
• Neglects the influence of concentration variations in the electrolyte
• Tertiary current distribution

– Accounts for Ohmic effects, effects of electrode kinetics, and the effects of conc
entration variations on the performance of a cell
62
Modeling of Electrochemical Cells
• Non-porous electrodes
– Heterogeneous reactions
– Typically used for electrolysis, metal winning, and electrodeposition
• Porous electrodes
– Reactions treated as homogeneous reaction in models although they are heterogeneous in reality
– Typically used for batteries, fuel cells, and in some cases also for electrolysis
• Electrolytes
– Diluted and supporting electrolytes
– Concentrated electrolytes
– ”Free” electrolytes with forced and free convection
– ”Immobilized” electrolytes through the use of porous matrixes, negligible free convection, rarely force
d convection
– Solid electrolytes, no convection
Primary Current Distribution

• Assumptions:
– Perfectly mixed
electrolyte
– Negligible activation overpotential
– Negligible ohmic losses in the anode
structure Anode: Wire electrode
Cathodes: Flat-plate
electrodes
Electrolyte
Cathodes: Flat-plate
electrodes
63
Domain and Boundary Settings
• Domain:
– Charge continuity Anode:
Cell voltage = 1.3 V
E0 = 1.2 V
• Boundary Total cell (in this case ohmic)
– Electrode potentials polarization = 100 mV
at electrode surfaces
– Insulation elsewhere
Cathodes: 0 V
Electrolyte:
Cathodes:
Electrode potential = 0 V N I l 0
E0 = 0 V
(negligible overpotential) I l
Ionic potential
Some Definitions
• Activation and concentration over
er
potential = 0 Il ,c 0 E0,c
K 0 Il ,a Ecell E0,a
K Is Il E0
I Ionic potential
Il Is E0 l
I Electronic potential
• Select the cathode as reference p s
oint Ecell Cell voltage
Is , c 0 Ia At anode, index
Ecell Is , a Is , c Ic At cathode, index
64
Results
• Current density distribution at tha ͻ Potential distribution in the
anode surface electrolyte
Hi hl active
Highly acctive
i catalyst
l
Inactive catalyst
Secondary Current Distribution

• Activation overpotential taken int • New boundary conditions
o account
K Is Il E0 N I n
l
ict
• Charge transfer current at the elec
trode surfaces
§ § 1 E FK · § E FK · ·
ict i0 ¨ exp ¨
¨ Rg T ¸¸ exp ¨¨ ¸¸ ¸
¨ R T ¸
© © ¹ © g ¹¹
Exchange current densityy Gas constant
stant
Faraday’s constant Charge transfer coefficient
65
Comparison: Primary and Secondary C
urrent Distributions
• Current density distribution at the ͻ Polarization curves
anode surface
Solid line = Primary

Dashed line = Secondary
Effect of
Activation
overpotential
Lower current density with equal

cell voltage (1.3V) compared to
primary case
Comparison: Primary and Secondary Current Density Dis

tribution, 0.1 A Total Current
• Dimensionless current density disr • Dimensionless current density disr
ibution, primary case ibution, secondary case
Independent of Dependent
total current of total current
ict
cdd
ict ,average
66
Tertiary Current Density Distribution
• Use the secondary current distribution case as starting point
• Add the flow equations, in this case from single phase laminar flow Navier-Stokes
• Solve only for the flow
• Add equations for mass transport, in this chase the Nernst-Planck equations
• Introduce the concentration dependence on the reaction kinetics
• Solve the fully coupled material and charge balances using the already solved flow fi
eld
Results: Concentration and Current De

nsity Distribution
Main direction of the flow Stagnation in the flow

results in lower concentration
67
Comparison: Primary, Secondary,
Tertiary Current Distributions
68
Wire Electrode
One of the most important aspects in the design of electrochemical cells is the current
density distributions in the electrolyte and electrodes. Non-uniform current density
distributions can be detrimental for the operation of electrochemical processes. In
many cases the parts of an electrode that are subjected to high current density degrade
at a faster rate. Knowledge of the current density distribution is also desired to
optimize the utilization of the electrocatalysts, because these are often made of
expensive noble metals. Non-uniform deposition and consumption, as well as
unnecessarily high overvoltages, with resulting energy losses and possibly unwanted
side-reactions, may be other effects that one would like to minimize.
This example models the primary, secondary, and tertiary current density
distributions (Ref. 1) of an arbitrary electrochemical cell. It successively goes through
the different classes of current density distributions so as to also show how complexity
should be gradually introduced when modeling electrochemical cells.
Introduction
The same geometry is considered in all three cases: a wire electrode structure is placed
between two flat electrode surfaces, and in the open volume between the wire and the
flat surfaces electrolyte is allowed to flow; see Figure 1. The electrochemical cell can
be seen as a unit cell of a larger wire-mesh electrode—an electrochemical cell setup
common for many large-scale industrial processes.
1 | WIRE ELECTRODE
69
.
Wire electrode Outlet
(anode)
Flat electrode
(cathode)
Flat electrode
(cathode)
Inlet
Figure 1: Modeled electrochemical cell. Wire electrode (anode) between two flat electrodes
(cathodes). Flow inlet to the left, outlet to the right. The top and bottom flat surfaces are
inert.
Model Definition
PRIMARY CURRENT DISTRIBUTION

Figure 1 shows the investigated geometry. Firstly, this example considers primary
current density distribution. This is the situation where the mixing of electrolyte is
vigorous or where concentration gradients are small, so that ionic migration is the
dominating transport mechanism. The general mass balance in the electrolyte,
assuming steady-state conditions and that no homogeneous reactions occur, can be
given by
∇ ⋅ Ni = 0
where Ni is the flux of species i (SI unit: mol·m2/s), which in turn is governed by:
– D i ∇c i – z i m i Fc i ∇φ l + c i u = N i (1)
where ci represents the concentration of the ion i (SI unit: mol/m3), zi its valence, Di
its diffusivity (SI unit: m2/s), mi its mobility (SI unit: mol·m2(s·V·A)), F denotes the
2 | WIRE ELECTRODE
70
Faraday constant (SI unit: As/mol), φ i the ionic potential, and u the velocity vector
(SI unit: m/s). The components operated upon by the above transport equation are
often described as the diffusion, migration, and convection transport mechanisms. The
net current density can be described through:
i = –F ¦ zi Ni
where i is the current density vector (SI unit: A/m2). Combining the three above
equations, while assuming electroneutrality (which removes the convection term) and
negligible concentration gradients (which removes diffusion) leaves:
2
i = –F ¦ –zi mi Fci ∇φl
Current density is conserved throughout:
∇⋅i = 0 (2)
so that by combining the valence, ionic mobility, constant concentration and the
Faraday constant to a representative conductivity, κ (SI unit: 1/(W·m2)), Equation 2
becomes:
∇ ⋅ ( – κ∇φ l ) = 0 (3)
This final equation is basically Ohm’s Law.
The boundary conditions for the case of primary current density distribution assume
that the kinetics on the electrode surfaces are fast, which allow the assumption of
constant potential on these surfaces (all other boundaries are insulated). The solid
phase (electronic conductor) potential on the cathode, φ s, c (SI unit: V), is a
convenient choice of reference potential in the system:
φ s, c = 0
The electrode potential equals the difference between the potential of solid phase in
the electrode, φ e , and the potential in the adjacent electrolyte, φ i :
E electrode = φ s – φ l
In the absence of kinetic losses, the cathode potential, Ec, equals the equilibrium
potential, Eeq,c:
E eq, c = φ s, c – φ l, c = – φ l, c
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which sets the boundary condition for the cathode.
The potential difference over the whole cell, Ecell, is defined as the potential difference
between the solid phases of the two electrodes
E cell = φ s, a – φ s, c = φ s, a
In this way the boundary condition for the ionic potential at the anode can be set via:
E eq, a = φ s, a – φ l, a = E cell – φ l, a
SECONDARY CURRENT DISTRIBUTION

Secondary current distribution takes into account the kinetics at the electrodes. Mixing
is supposed to be good and the electroneutrality condition still relevant so that Ohm’s
Law remains a good description for the equations in the domain. Yet the
electrochemical reactions are no longer fast enough that a constant potential can be
applied at the electrodes. The properties of the chemical species and their ability to
react at the surface, that is, the reaction driving forces (overvoltages), need to be
considered.
In this model, the expressions for the local current density, i (SI unit: A/m2), is based
on the Butler-Volmer equation (Ref. 2) for a single electron reaction. For the
secondary current distribution case (that is, without concentration dependence) it
reads:
i loc = i 0 ( exp ( η ( 1 – β )F ⁄ ( RT ) ) – exp ( ηβF ⁄ ( RT ) ) )
here T is the temperature and R is the gas constant (SI unit: J/(K·mol). i0, the
exchange current density, (SI unit: A/m2), and β, the symmetry factor, are reaction
and electrode dependent and are therefore different for each electrode. The
overpotential, η, is the difference between the electrode potential and the equilibrium
potential for the electrode reaction, defined in the following way:
η = E electrode – E eq
This results in the following expressions for the overpotentials for the cathode and
anode, respectively:
η c = – φ l, c – E eq, c
η a = E cell – φ l, a – E eq, a
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TERTIARY CURRENT DISTRIBUTION

In tertiary current density distribution, mass transport through diffusion, convection,
and migration has to be considered (that is, all components of Equation 1).
For the net ionic charge transport the assumption for this model still is
electroneutrality and a supporting electrolyte with negligible concentration gradients,
which means that the potential distribution in the electrolyte can be described through
Ohm’s Law (Equation 3)
To introduce a mass transport dependence in this model the species being oxidized at
the anode now has mass transport limitations and its localized concentration, c
(SI unit: mol/m3), affects the electrode kinetics. The anodic branch of the
Butler-Volmer expression at the anode therefore gets a concentration dependence, and
the expression now reads:
c
i a = i 0 §© ----- exp ( η ( 1 – β )F ⁄ ( RT ) ) – exp ( ηβF ⁄ ( RT ) )·¹ (4)
c0
Here c0 (SI unit: mol/m3) denotes a reference concentration (equal to the inlet
concentration). Equation 4 is applied to the wire (anode) electrode, while the cathodes
keep the expression for the local current density from the secondary current
distribution model.
Also a momentum balance is introduced to describe the convection. In this case, the
assumption is a stationary laminar incompressible flow, using the Navier-Stokes
equation:
T
– ∇ ⋅ μ ( ∇u + ( ∇u ) ) + ρ ( u ⋅ ∇ )u + ∇p = 0 (5)
∇⋅u = 0
where μ is the dynamic viscosity (SI unit: Ns/m2), ρ density (SI unit: kg/m3) and p
pressure (SI unit: Pa).
No Slip boundary conditions are applied to the electrode surfaces, and slip boundary
conditions to the top and bottom to account for the periodically repeating unit cell in
this spatial direction. At the inlet, a laminar inflow with a fixed mean velocity is
specified, whereas a pressure condition specifying a zero reference pressure is used at
the outlet.
Finally, Equation 1 accounts for the mass transport of the reacting species:
∇ ⋅ ( – D∇c – zmFc∇φ + cu ) = 0 (6)
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No-flux boundary conditions are applied for all boundaries except for the inlet, outlet
and the anode. At the inlet, a fixed concentration is specified. Outflow conditions are
applied for the outlet. Faraday’s law is used to specify the net molar flux at the anode
where the species is consumed:
ia
N a = – ----
F

Figure 2 shows the different polarization plots that results from using a parametric
solver to solve for all the three cases of current distribution. The total current decreases
as potential losses due to kinetics and mass transport are introduced in the model. The
following sections cover each case more in detail.
Figure 2: Polarization plots comparing the three cases of current distribution.
PRIMARY CURRENT DISTRIBUTION

Figure 3 shows the potential distribution in the electrolyte and current density
distribution at the anode at a cell voltage of 1.45 V. The current density distribution is
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highest at the corners of the wires and close to zero at the central parts of the wire
structure.
Figure 3: Primary current distribution, Ecell=1.45 V. Potential distribution in the

electrolyte (top) and current density on the anode (bottom).
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SECONDARY CURRENT DISTRIBUTION

Figure 4 shows the plots for the secondary current distribution. A higher cell voltage
is chosen reach a total cell current comparable to Figure 3. Compared to the primary
current distribution the secondary current distribution is smoother, this is due to the
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effect that a high local current density induces local over potential losses on the
electrode surface.
Figure 4: Secondary current distribution, Ecell=1.65 V. Potential distribution in the

electrolyte (left) and current density on the anode (right).
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TERT IA RY CUR REN T D SIT RIBUTIO N

Figure 5 shows the flow velocity magnitude of the flow and the concentration of the
reactant at 1.8 V. The convective flow is close to zero between the wires, and this
results in a depletion zone with low concentration in these parts in the cell.
Figure 5: Flow field (top: slice plot, right: arrows) and concentration profile (bottom: slices
and anode surface) at 1.8 V.
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Figure 6 shows the resulting potential and current density distribution. The low
concentration between the wires now impacts severely on the smoothness of the
current distribution.
Figure 6: Tertiary current distribution, Ecell=1.8 V. Potential distribution in the

electrolyte (top) and current density on the anode (bottom).
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Notes About the COMSOL Implementation

You set up the model using the following physics interfaces:
• Primary Current Distribution for modeling the electrolyte potential, governed by

Ohm’s Law (Equation 3). The secondary and tertiary current distributions are
modeled by changing the current distribution type of the interface to Secondary.
• Transport of Diluted Species for the mass transport of the reacting species
(Equation 6).
• Laminar Flow for the momentum balance to describe the convection (Equation 5).
References
1. J.S. Newman, Electrochemical Systems, 2nd ed., Prentice Hall, NJ, 1990.
2. J. O’M. Bockris and A.K.N. Reddy, Modern Electrochemistry, Plenum Press, NY,
1970.
Application Library path: Electrochemistry_Module/

Electrochemical_Engineering/wire_electrode
NEW
MODEL WIZARD
2 In the Select physics tree, select Electrochemistry>Primary Current Distribution (siec).
3 Click Add.
4 Click Study.
5 In the Select study tree, select Preset Studies>Stationary.
6 Click Done.
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GEOMETRY 1
Import the model geometry from a file.
Import 1 (imp1)
1 On the Home toolbar, click Import.
2 In the Settings window for Import, locate the Import section.
3 Click Browse.
wire_electrode.mphbin.
5 On the Home toolbar, click Build All.
DEFINITIONS
Create selections for the anode and the cathode in the geometry. They will be used
later when setting up the physics.
Explicit 1
4 Select Boundaries 2 and 5 only.
5 Right-click Component 1 (comp1)>Definitions>Explicit 1 and choose Rename.
6 In the Rename Explicit dialog box, type Cathodes in the New label text field.
7 Click OK.
Explicit 2
4 Select the All boundaries check box.
5 Select Boundaries 6–37 only. This selection is easiest to achieve by selecting all
boundaries (the 'All boundaries' check box), followed by deselecting all exterior
surfaces.
7 In the Rename Explicit dialog box, type Anode in the New label text field.
8 Click OK.
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Create some component couplings to be used when analyzing the results.

2 In the Settings window for Integration, type anode_int in the Operator name text
field.
3 Locate the Source Selection section. From the Geometric entity level list, choose
Boundary.
4 From the Selection list, choose Anode.
Average 1 (aveop1)
1 On the Definitions toolbar, click Component Couplings and choose Average.
2 In the Settings window for Average, type anode_avg in the Operator name text field.
3 Locate the Source Selection section. From the Geometric entity level list, choose
Boundary.
GLOBAL DEFINITIONS
Now start defining the physics for the primary current distribution simulation. Begin
with the model parameters.
Parameters

Ecell 1.3[V] 1.3 V Cell voltage
Eeq_c 0[V] 0V Cathode equilibrium
potential
Eeq_a 1.2[V] 1.2 V Anode equilibrium
potential
MATERIALS
Add water from the material library. Modify the material by adding the conductivity
value.
ADD MATERIAL
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3 In the tree, select Built-In>Water, liquid.
MATERIALS
Water, liquid (mat1)

1 In the Model Builder window, under Component 1 (comp1)>Materials click Water,
liquid (mat1).
2 In the Settings window for Material, locate the Material Contents section.
Property Name Value Unit Property group

Electrolyte conductivity sigmal 10[S/ S/m Electrolyte conductivity
m]
4 Right-click Component 1 (comp1)>Materials>Water, liquid (mat1) and choose

Rename.
5 In the Rename Material dialog box, type Electrolyte in the New label text field.
6 Click OK.
PRIMARY CURRENT DISTRIBUTION (SIEC)
Electrolyte 1
Now start setting up the physics. Only the equilibrium potentials and the electrode
potential boundary values need to be set for the primary current distribution.
Electrolyte-Electrode Boundary Interface 1

1 On the Physics toolbar, click Boundaries and choose Electrolyte-Electrode Boundary
Interface.
2 In the Settings window for Electrolyte-Electrode Boundary Interface, locate the
Boundary Selection section.
3 From the Selection list, choose Cathodes.
Electrode Reaction 1
1 In the Model Builder window, expand the Electrolyte-Electrode Boundary Interface 1
node, then click Electrode Reaction 1.
2 In the Settings window for Electrode Reaction, locate the Model Inputs section.
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3 In the T text field, type T.

4 Locate the Equilibrium Potential section. In the Eeq text field, type Eeq_c.
Electrolyte-Electrode Boundary Interface 2

1 On the Physics toolbar, click Boundaries and choose Electrolyte-Electrode Boundary
Interface.
2 In the Settings window for Electrolyte-Electrode Boundary Interface, locate the
4 Locate the Boundary Condition section. In the φs,ext text field, type Ecell.
1 In the Model Builder window, expand the Electrolyte-Electrode Boundary Interface 2
node, then click Electrode Reaction 1.
2 In the Settings window for Electrode Reaction, locate the Model Inputs section.
4 Locate the Equilibrium Potential section. In the Eeq text field, type Eeq_a.
Initial Values 1
Also, provide initial values for the electrolyte potential.
1 In the Model Builder window, under Component 1 (comp1)>Primary Current

Distribution (siec) click Initial Values 1.
2 In the Settings window for Initial Values, locate the Initial Values section.
3 In the phil text field, type (Ecell-Eeq_a-Eeq_c)/2.
MESH 1
The following steps creates a mesh with boundary layers adjacent to the anode and
cathode surfaces. This is a convenient way of increasing the number of mesh elements
close to a surface of special interest.
Boundary Layer Properties

1 In the Model Builder window, under Component 1 (comp1) right-click Mesh 1 and
choose Boundary Layers.
2 In the Settings window for Boundary Layer Properties, locate the Boundary Selection
section.
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4 Locate the Boundary Layer Properties section. In the Number of boundary layers text
field, type 6.
5 In the Boundary layer stretching factor text field, type 1.3.
6 From the Thickness of first layer list, choose Manual.
7 In the Thickness text field, type 2e-5.
Boundary Layer Properties 1

1 In the Model Builder window, under Component 1 (comp1)>Mesh 1 right-click
Boundary Layers 1 and choose Boundary Layer Properties.
2 In the Settings window for Boundary Layer Properties, locate the Boundary Selection
section.
3 From the Selection list, choose Cathodes.
4 Locate the Boundary Layer Properties section. In the Number of boundary layers text
field, type 2.
5 In the Boundary layer stretching factor text field, type 1.3.
6 In the Thickness adjustment factor text field, type 5.
Size
1 In the Model Builder window, under Component 1 (comp1)>Mesh 1 click Size.
2 In the Settings window for Size, locate the Element Size section.
3 From the Calibrate for list, choose Fluid dynamics.
STUDY 1
The model is now ready for solving. Add an auxiliary continuation sweep to solve for
a range of cell potentials.
Step 1: Stationary
2 In the Settings window for Stationary, click to expand the Study extensions section.
3 Locate the Study Extensions section. Select the Auxiliary sweep check box.
4 Click Add.
Parameter name Parameter value list Parameter unit

Ecell range(1.25,0.05,1.8)
6 In the Model Builder window, click Study 1.
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You have now solved the primary current distribution model.
RESULTS
Data Sets
To be able to study the anode surface in detail, create a selection of the solution.
1 On the Results toolbar, click More Data Sets and choose Solution.
2 On the Results toolbar, click Selection.
3 In the Settings window for Selection, locate the Geometric Entity Selection section.
STUDY 1
Solution 1 and 2 in the data sets will now be updated every time you update and solve
the model. To store this particular solution, copy and store the primary current
distribution solution in order to compare with these results later when you modify the
model.
Solution 1
In the Model Builder window, expand the Study 1>Solver Configurations node.
Solution 1 - Copy 1
1 Right-click Solution 1 and choose Solution>Copy.
2 In the Model Builder window, under Study 1>Solver Configurations right-click Solution
1 - Copy 1 and choose Rename.
3 In the Rename Solution dialog box, type Primary current distribution in the
New label text field.
4 Click OK.
RESULTS
Data Sets
2 In the Settings window for Solution, locate the Solution section.
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3 From the Solution list, choose Primary current distribution.

1D Plot Group 1
Now create a polarization plot for the primary current distribution model.
1 On the Results toolbar, click 1D Plot Group.

3 From the Data set list, choose None.
4 Click to expand the Title section. From the Title type list, choose Manual.
5 In the Title text area, type Polarization plot.
6 Locate the Plot Settings section. Select the x-axis label check box.
7 In the associated text field, type Cell voltage (V).
8 Select the y-axis label check box.
9 In the associated text field, type Total current (A).
10 Click to expand the Legend section. From the Position list, choose Upper left.
11 On the 1D Plot Group 1 toolbar, click Global.
12 In the Settings window for Global, locate the Data section.
13 From the Data set list, choose Study 1/Primary current distribution (3).
14 Locate the y-Axis Data section. In the table, enter the following settings:
Expression Unit Description

abs(anode_int(siec.nIl)) A
15 Click to expand the Legends section. From the Legends list, choose Manual.
Legends
Primary current distribution
3D Plot Group 2
The following creates an isosurface of the potential in the electrolyte.
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4 Right-click Results>3D Plot Group 2 and choose Isosurface.
5 In the Settings window for Isosurface, locate the Data section.
6 From the Data set list, choose Study 1/Solution 1 (1).
7 From the Parameter value (Ecell) list, choose 1.45.
3D Plot Group 3
The following creates a normalized plot of the normal electrolyte current density on
the anode surface.
4 Click to expand the Title section. From the Title type list, choose Manual.
5 In the Title text area, type Dimensionless current density distribution.
6 Locate the Plot Settings section. Clear the Plot data set edges check box.
8 In the Settings window for Surface, locate the Data section.
Plot the normal current density divided by the average normal current density.
11 Locate the Expression section. In the Expression text field, type (comp1.siec.nIl)/
anode_avg(comp1.siec.nIl).
PRIMARY CURRENT DISTRIBUTION (SIEC)

Now modify the model to simulate the secondary current distribution.
1 In the Model Builder window, under Component 1 (comp1) click Primary Current
Distribution (siec).
2 In the Settings window for Primary Current Distribution, locate the Current
Distribution Type section.
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3 From the Current distribution type list, choose Secondary.
GLOBAL DEFINITIONS
Add the needed parameters for the secondary model.
Parameters
1 In the Model Builder window, under Global Definitions click Parameters.

i0_c 100[A/m^2] 100 A/m² Cathode exchange
current density
i0_a 100[A/m^2] 100 A/m² Anode exchange current
density
be_c 0.5 0.5 Cathode symmetry factor
be_a 0.5 0.5 Anode symmetry factor
T 298[K] 298 K Temperature
SECONDARY CURRENT DISTRIBUTION (SIEC)

On the Physics toolbar, click Primary Current Distribution (siec) and choose Secondary
Current Distribution (siec).
Now set up the new boundary conditions for the secondary current distribution by
adding the needed kinetics parameters.
1 In the Model Builder window, under Component 1 (comp1)>Secondary Current

Distribution (siec)>Electrolyte-Electrode Boundary Interface 1 click Electrode Reaction
1.
2 In the Settings window for Electrode Reaction, locate the Electrode Kinetics section.
3 From the Kinetics expression type list, choose Butler-Volmer.
4 In the i0 text field, type i0_c.
5 In the αa text field, type be_c.
6 In the αc text field, type 1-be_c.
7 In the Model Builder window, click Electrode Reaction 1.
9 From the Kinetics expression type list, choose Butler-Volmer.
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10 In the i0 text field, type i0_a.

11 In the αa text field, type be_a.
12 In the αc text field, type 1-be_a.
STUDY 1
On the Home toolbar, click Compute.
RESULTS
3D Plot Group 2
You have now solved the secondary current distribution problem.
STUDY 1
Solution 1
1 In the Model Builder window, under Study 1>Solver Configurations right-click Solution
1 and choose Rename.
2 In the Rename Solution dialog box, type Secondary current distribution in the
3 Click OK.
RESULTS
Proceed to look at the results by adding the secondary current distribution
polarization plot.
1D Plot Group 1
1 In the Model Builder window, under Results>1D Plot Group 1 right-click Global 1 and
choose Duplicate.
3 From the Data set list, choose Study 1/Secondary current distribution (1).
4 Locate the Legends section. In the table, enter the following settings:
Legends
Secondary current distribution

Note that you have now updated the 3D plots to contain the results from the latest
computation. (By choosing different data sets you may compare the primary and
secondary current distribution results.)
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3D Plot Group 2
1 In the Model Builder window, under Results>3D Plot Group 2 click Isosurface 1.
3D Plot Group 3
1 In the Model Builder window, under Results>3D Plot Group 3 click Surface 1.
GLOBAL DEFINITIONS
Now modify the problem to model a tertiary current distribution problem by adding
mass transport. Start by adding the parameters.
Parameters
1 In the Model Builder window, under Global Definitions click Parameters.

D 1e-9[m^2/s] 1E-9 m²/s Diffusion coefficient
c_in 1e3[mol/m^3] 1000 mol/m³ Inlet concentration
u_in 5[mm/s] 0.005 m/s Inlet flow velocity
DEFINITIONS
Explicit 3
3 In the Rename Explicit dialog box, type Inlet in the New label text field.
4 Click OK.
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Explicit 4
3 In the Rename Explicit dialog box, type Outlet in the New label text field.
4 Click OK.
ADD PHYSICS
3 In the Add physics tree, select Chemical Species Transport>Transport of Diluted Species
(tds).
ADD PHYSICS
2 In the Add physics tree, select Fluid Flow>Single-Phase Flow>Laminar Flow (spf).
1 In the Model Builder window, under Component 1 (comp1) click Transport of Diluted
Species (tds).
2 In the Settings window for Transport of Diluted Species, locate the Transport
Mechanisms section.
3 Select the Migration in electric field check box.
1 In the Model Builder window, expand the Transport of Diluted Species (tds) node, then
click Transport Properties 1.
2 In the Settings window for Transport Properties, locate the Model Inputs section.
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3 From the u list, choose Velocity field (spf).

5 In the V text field, type phil.
6 Locate the Diffusion section. In the Dc text field, type D.
7 Locate the Migration in Electric Field section. In the zc text field, type -1.
Inflow 1
1 On the Physics toolbar, click Boundaries and choose Inflow.
2 In the Settings window for Inflow, locate the Boundary Selection section.
4 Locate the Concentration section. In the c0,c text field, type c_in.
Outflow 1
Initial Values 1
1 In the Model Builder window, under Component 1 (comp1)>Transport of Diluted
Species (tds) click Initial Values 1.
3 In the c text field, type c_in.
Electrode-Electrolyte Interface Coupling 1

Couple the flux on the anode surface to the electrode reaction currents by using a
Electrode-Electrolyte Interface Coupling feature.
1 On the Physics toolbar, click Boundaries and choose Electrode-Electrolyte Interface

Coupling.
2 In the Settings window for Electrode-Electrolyte Interface Coupling, locate the
Reaction Coefficients 1
1 In the Model Builder window, expand the Electrode-Electrolyte Interface Coupling 1
node, then click Reaction Coefficients 1.
2 In the Settings window for Reaction Coefficients, locate the Model Inputs section.
3 From the iloc list, choose Local current density (siec/eebii2/er1).
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4 Locate the Stoichiometric Coefficients section. In the νc text field, type 1.
SECONDARY CURRENT DISTRIBUTION (SIEC)

Also modify the current density expression to be concentration dependent.
On the Physics toolbar, click Transport of Diluted Species (tds) and choose Secondary
Current Distribution (siec).
1 In the Model Builder window, under Component 1 (comp1)>Secondary Current
Distribution (siec)>Electrolyte-Electrode Boundary Interface 2 click Electrode Reaction
1.
3 From the Kinetics expression type list, choose Concentration dependent kinetics.
4 In the CR text field, type c/c_in.
LAMINAR FLOW (SPF)

On the Physics toolbar, click Secondary Current Distribution (siec) and choose Laminar
Flow (spf).
Fluid Properties 1
1 In the Model Builder window, under Component 1 (comp1)>Laminar Flow (spf) click
Fluid Properties 1.
2 In the Settings window for Fluid Properties, locate the Model Inputs section.
Inlet 1
2 In the Settings window for Inlet, locate the Boundary Selection section.
4 Locate the Boundary Condition section. From the list, choose Laminar inflow.
5 Locate the Laminar Inflow section. In the Uav text field, type u_in.
6 In the Lentr text field, type 10e-3.
Outlet 1
2 In the Settings window for Outlet, locate the Boundary Selection section.
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4 Locate the Pressure Conditions section. Select the Normal flow check box.
Wall 2
1 On the Physics toolbar, click Boundaries and choose Wall.
2 Select Boundaries 3 and 4 only.
3 In the Settings window for Wall, locate the Boundary Condition section.
4 From the Boundary condition list, choose Slip.
ADD STUDY
Next, set up the solver for the tertiary current distribution problem. Do this by adding
a new study wherein you first solve for the flow problem, which does not depend on
the other variables, and then the species transport and electric currents.
STUDY 2
Step 1: Stationary
2 In the Settings window for Stationary, locate the Physics and Variables Selection
section.
Physics interface Solve for Discretization

Secondary Current Distribution physics
Transport of Diluted Species physics
Step 2: Stationary 2
1 On the Study toolbar, click Study Steps and choose Stationary>Stationary.
2 In the Settings window for Stationary, locate the Physics and Variables Selection
section.
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Physics interface Solve for Discretization

Laminar Flow physics
Set up an auxiliary continuation sweep for the 'Ecell' parameter.

4 Click to expand the Study extensions section. Locate the Study Extensions section.
Select the Auxiliary sweep check box.
5 Click Add.
Parameter name Parameter value list Parameter unit

Ecell range(1.25,0.05,1.8)
Solution 3
Change to a fully coupled direct solver to decrease solver time.

3 In the Model Builder window, expand the Study 2>Solver Configurations>Solution
3>Stationary Solver 2 node.
4 Right-click Study 2>Solver Configurations>Solution 3>Stationary Solver 2 and choose
Fully Coupled.
5 In the Settings window for Fully Coupled, locate the General section.
6 From the Linear solver list, choose Direct 1.
You have now solved the tertiary current distribution.
11 Right-click Study 2 and choose Rename.
12 In the Rename Study dialog box, type Tertiary current distribution in the
13 Click OK.
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RESULTS
Data Sets
Add the tertiary current distribution to the polarization plot.
1D Plot Group 1
1 In the Model Builder window, under Results>1D Plot Group 1 right-click Global 2 and
choose Duplicate.
3 From the Data set list, choose Tertiary current distribution/Solution 3.
4 Locate the Legends section. In the table, enter the following settings:
Legends
Tertiary current distribution
Data Sets
2 In the Settings window for Solution, locate the Solution section.
3 From the Solution list, choose Solution 3.
3D Plot Group 4
3 From the Data set list, choose Tertiary current distribution/Solution 3 (5).
4 Right-click Results>3D Plot Group 4 and choose Slice.
5 In the Settings window for Slice, click Replace Expression in the upper-right corner
of the Expression section. From the menu, choose Component 1>Laminar Flow>spf.U
- Velocity magnitude.
6 Locate the Plane Data section. In the Planes text field, type 7.
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3D Plot Group 5
Finish the post-processing by creating a arrow, slice and surface plot that visualizes the
concentration and flow in the cell.
4 Locate the Plot Settings section. Clear the Plot data set edges check box.
5 Right-click Results>3D Plot Group 5 and choose Arrow Volume.
6 In the Settings window for Arrow Volume, click Replace Expression in the upper-right
corner of the Expression section. From the menu, choose Component 1>Laminar
Flow>u,v,w - Velocity field.
7 Locate the Arrow Positioning section. Find the x grid points subsection. In the Points
text field, type 15.
8 Find the y grid points subsection. In the Points text field, type 15.
9 Find the z grid points subsection. In the Points text field, type 1.
10 Locate the Coloring and Style section. From the Color list, choose Black.
11 Select the Scale factor check box.
12 In the associated text field, type 0.1.
13 Right-click Results>3D Plot Group 5>Arrow Volume 1 and choose Duplicate.
14 In the Settings window for Arrow Volume, locate the Arrow Positioning section.
15 Find the y grid points subsection. In the Points text field, type 1.
16 Find the z grid points subsection. In the Points text field, type 15.
18 On the 3D Plot Group 5 toolbar, click More Plots and choose Multislice.
19 In the Settings window for Multislice, click Replace Expression in the upper-right
corner of the Expression section. From the menu, choose Component 1>Transport of
Diluted Species>c - Concentration.
20 Locate the Multiplane Data section. Find the x-planes subsection. In the Planes text
field, type 0.
21 In the Model Builder window, right-click 3D Plot Group 5 and choose Surface.
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24 Click Replace Expression in the upper-right corner of the Expression section. From
the menu, choose Component 1>Transport of Diluted Species>c - Concentration.
25 Click to expand the Inherit style section. Locate the Inherit Style section. From the
Plot list, choose Multislice 1.
3D Plot Group 2
1 In the Model Builder window, under Results>3D Plot Group 2 click Isosurface 1.
3D Plot Group 3
1 In the Model Builder window, under Results>3D Plot Group 3 click Surface 1.
31 | WIRE ELECTRODE
99
&MFDUSPEFQPTJUJPOPG
*OEVDUPS$PJM
100
Electrodeposition of
an Inductor Coil
Model
101
Physics
Electrode reaction:
Deposition growth rate:
Equations: Electrodeposition, Secondary Interface

+ Transport of Diluted Species Interface
Results
102
Electrodeposition of an Inductor Coil

Introduction
This example models the deposition of an inductor coil in the μm-scale, where
diffusion limitations govern the deposition rate. A 10 μm thick photoresist mask has
been used create the deposition pattern. As the deposition process proceeds, the depth
of the pattern created by the mask decreases, which in turn affects the current
distribution over the active surface.
Model Definition
The model geometry is shown in Figure 1. The geometry consists of two domains: the
10 μm extrusion of the deposition pattern down into the photoresist film, and a
diffusion layer in form of a rectangular block, 50 μm thick, on top of the photoresist.
Cathode
Diffusion layer
Photoresist
Figure 1: Model geometry. The extruded spiral pattern forms the vertical photoresist walls,
10 μm high. The diffusion layer, in form of a rectangular block, is 50 μm thick.
1 | ELECTRODEPOSITION OF AN INDUCTOR COIL

103
CURRENT CONDUCTION, ELECTROCHEMICAL REACTIONS, AND

GEOMETRY DEFORMATION
Assume the electrolyte to consist of CuSO4 in a H2SO4 supporting electrolyte with a
conductivity of 10 S/m. The presence of a supporting electrolyte with a constant
conductivity implies a secondary current distribution with regards to the charge
transport. Use an Electrodeposition, Secondary interface to model the current
distribution, solving for the electrolyte potential φ l , and the geometry deformation
due to the metal deposition on the cathode.
On the top boundary, set the electrolyte potential to 0 V. On the bottom boundary,
the cathode, the electrode reaction
2+ -
Cu (l) + 2e = Cu(s)
follows the following kinetics expression for the charge transfer current ict:
§ 1.5Fη c Cu2+ 0.5Fη ·

i ct = i 0 ¨ exp §© ----------------·¹ – --------------------- exp § – ----------------· ¸
© RT c Cu 2+ ,ref © RT ¹ ¹
where i0 is the exchange current density (10 A/m2), η the overpotential, F Faraday’s
constant (96485 C/mol), R the molar gas constant (8.13 J/(mol·K)), T the
temperature, c Cu 2+ the electrolyte copper ion concentration (mol/m3), and c Cu 2+ ,ref ,
the reference copper concentration in the bulk electrolyte (500 mol/m3).
Set the current density of the cathode to have an average value of 10 A/dm2. All
boundaries except the cathode and the top bulk electrolyte boundary are isolated.
The electrode reaction causes the electrode boundary to move in the normal direction
with a velocity vdep (m/s) according to
M Cu i ct
v dep = – ----------- -------
ρ Cu 2F
where MCu is the molar mass (0.06355 kg/mol) and ρCu the density (8960 kg/m3)
of copper, respectively.
The extruded pattern domain is allowed deform according to the electrode boundary
deposition rate, whereas the diffusion layer domain is set to be fixed. The vertical walls
of the photoresist are fixed in the x and y directions, whereas the internal boundary
between the fixed and free moving domain is set to have zero deformation in the
z direction.

104
TR A N S P O R T O F C O P P E R I O N S I N T H E E L E C T RO L Y T E
The transport of copper ions in the electrolyte is described by Fickian diffusion. Model
this transport using a Transport of Diluted Species interface, solving for the electrolyte
copper ion concentration, c Cu 2+ . Set the diffusion coefficient to 10−9 m2/s.
At the top electrolyte bulk boundary, set the concentration the bulk
concentration c Cu 2+ ,ref . On the cathode, couple the flux of ions, N Cu 2+ (mol/(m2·s)),
to the electrochemical reactions via Faraday’s law:
i ct
N Cu 2+ = -------
2F
Assume No flux conditions for all other boundaries
Solve the problem using a time-dependent study, investigating the deposition during
180 s with an initial copper concentration in the electrolyte set to c Cu 2+ ,ref .

Figure 2 shows the concentration and current stream lines in the electrolyte after
180 s. The copper ion concentration at the cathode is significantly lower than in the
bulk. In addition, the concentration at the cathode is slightly higher in outer parts of
the pattern compared to the center.

105
Figure 2: Concentration profile and current stream lines in the electrolyte at t = 180 s.
Figure 3 shows the local electrode current, ict, at the cathode at t=180 s. The
deposition currents are higher at the outer parts of the pattern due to the higher
copper ion concentration.

106
Figure 3: Electrode reaction current density at t = 180 s.
Figure 4 shows the deformation and deposited copper thickness after 180 s. The
thickness is significantly thicker on the outermost part of the pattern.

107
Figure 4: Thickness of the deposited copper layer at 180 s.
Finally, the electrolyte potential for a cut plane at x = −1 μm is shown in Figure 5. The
electrolyte potential variation is relatively small for the modeled geometry

108
Figure 5: Electrolyte potential a long the plane x = −1 μm.
Notes About the COMSOL Implementation

By using a Nondepositing Boundary node on the vertical photoresist walls with the
boundary condition set to Zero Normal Displacement and with an additional given
line along which the deformation is allowed to occur, the number of degrees of
freedom for the problem gets reduced, and the solver performance is increased.
Application Library path: Electrodeposition_Module/Tutorials/

inductor_coil
NEW

109
MODEL WIZARD
2 In the Select physics tree, select Electrochemistry>Electrodeposition, Deformed
Geometry>Electrodeposition, Secondary (edsec).
3 Click Add.
4 In the Select physics tree, select Chemical Species Transport>Transport of Diluted
Species (tds).
5 Click Add.
6 Click Study.
7 In the Select study tree, select Preset Studies for Selected Physics Interfaces>Time
Dependent with Initialization.
8 Click Done.
GLOBAL DEFINITIONS
Load the model parameters from a text file.
Parameters
3 Click Load from File.
inductor_coil_parameters.txt.
Define two analytical functions that will be used when drawing the spirals in the
geometry.
Analytic 1 (an1)
1 On the Home toolbar, click Functions and choose Global>Analytic.
2 In the Settings window for Analytic, type spiralX in the Function name text field.
3 Locate the Definition section. In the Expression text field, type -(s/
(2*pi)*a_tot+R)*sin(s).
4 In the Arguments text field, type s, R.

5 Locate the Units section. In the Arguments text field, type 1, m.
6 In the Function text field, type m.
Analytic 2 (an2)
1 On the Home toolbar, click Functions and choose Global>Analytic.

110
2 In the Settings window for Analytic, type spiralY in the Function name text field.
3 Locate the Definition section. In the Expression text field, type -(s/
(2*pi)*a_tot+R)*cos(s).
4 In the Arguments text field, type s, R.

5 Locate the Units section. In the Arguments text field, type 1, m.
6 In the Function text field, type m.
GEOMETRY 1
Now draw the geometry. Start with the deposition pattern, using a work plane.
1 On the Geometry toolbar, click Work Plane.
Parametric Curve 1 (pc1)

1 On the Work Plane toolbar, click Primitives and choose Parametric Curve.
2 In the Settings window for Parametric Curve, locate the Parameter section.
3 In the Maximum text field, type w_tot.
4 Locate the Expressions section. In the xw text field, type spiralX(s,r0).
5 In the yw text field, type spiralY(s,r0).
Plane Geometry
Right-click Component 1 (comp1)>Geometry 1>Work Plane 1 (wp1)>Plane
Geometry>Parametric Curve 1 (pc1) and choose Build Selected.
Parametric Curve 2 (pc2)

1 On the Work Plane toolbar, click Primitives and choose Parametric Curve.
2 In the Settings window for Parametric Curve, locate the Parameter section.
3 In the Maximum text field, type w_tot.
4 Locate the Expressions section. In the xw text field, type spiralX(s,r0+a1).
5 In the yw text field, type spiralY(s,r0+a1).
Plane Geometry
Geometry>Parametric Curve 2 (pc2) and choose Build Selected.
Rectangle 1 (r1)
1 On the Work Plane toolbar, click Primitives and choose Rectangle.
3 In the Width text field, type a1.

111
4 In the Height text field, type 2*a1.

5 Locate the Position section. In the yw text field, type -r0-a1.
Plane Geometry
Geometry>Rectangle 1 (r1) and choose Build Selected.
Square 1 (sq1)
1 On the Work Plane toolbar, click Primitives and choose Square.
2 In the Settings window for Square, locate the Size section.
3 In the Side length text field, type 2*a1.
4 Locate the Position section. In the xw text field, type -a1/2.
5 In the yw text field, type -a1.
Plane Geometry
Geometry>Square 1 (sq1) and choose Build Selected.
Fillet 1 (fil1)
1 On the Work Plane toolbar, click Fillet.
2 On the object r1, select Point 2 only.
3 In the Settings window for Fillet, locate the Radius section.
4 In the Radius text field, type a1.
Plane Geometry
Geometry>Fillet 1 (fil1) and choose Build Selected.
Rectangle 2 (r2)
1 On the Work Plane toolbar, click Primitives and choose Rectangle.
3 In the Width text field, type a1.
4 In the Height text field, type 2*a1.
5 Locate the Position section. In the xw text field, type -a1.
6 In the yw text field, type -r0-2*a1-laps*a_tot.
Plane Geometry
Geometry>Rectangle 2 (r2) and choose Build Selected.

112
Square 2 (sq2)
1 On the Work Plane toolbar, click Primitives and choose Square.
2 In the Settings window for Square, locate the Size section.
3 In the Side length text field, type 2*a1.
4 Locate the Position section. In the xw text field, type -1.5*a1.
5 In the yw text field, type -r0-4*a1-laps*a_tot.
Plane Geometry
Geometry>Square 2 (sq2) and choose Build Selected.
Convert to Solid 1 (csol1)

1 On the Work Plane toolbar, click Conversions and choose Convert to Solid.
2 Click in the Graphics window and then press Ctrl+A to select all objects.
Work Plane 1 (wp1)

Geometry>Convert to Solid 1 (csol1) and choose Build Selected.
Extrude 1 (ext1)
1 On the Geometry toolbar, click Extrude.
2 In the Settings window for Extrude, locate the Distances from Plane section.
Distances (m)
d_pr
4 Right-click Component 1 (comp1)>Geometry 1>Extrude 1 (ext1) and choose Build

Selected.
Block 1 (blk1)
1 On the Geometry toolbar, click Block.
2 In the Settings window for Block, locate the Size section.
3 In the Width text field, type 2*(r0+a_tot*laps+d_dl).
4 In the Depth text field, type 2*(r0+a_tot*laps+d_dl)+3*a1.
5 In the Height text field, type d_dl.
6 Locate the Position section. In the y text field, type -2*a1.
7 In the z text field, type d_pr+d_dl/2.

113
8 From the Base list, choose Center.

9 Right-click Component 1 (comp1)>Geometry 1>Block 1 (blk1) and choose Build
Selected.
DEFINITIONS
Add a number of selections to facilitate domain and boundary selection when setting
up the physics.
1 Click the Transparency button on the Graphics toolbar.
Explicit 1
4 In the Rename Explicit dialog box, type Fixed domain in the New label text field.
5 Click OK.
Complement 1
1 On the Definitions toolbar, click Complement.
2 In the Settings window for Complement, locate the Input Entities section.
3 Under Selections to invert, click Add.
4 In the Add dialog box, select Fixed domain in the Selections to invert list.
5 In the Selections to invert list, select Fixed domain.
6 Click OK.
7 Right-click Component 1 (comp1)>Definitions>Complement 1 and choose Rename.
8 In the Rename Complement dialog box, type Deforming domain in the New label
text field.
9 Click OK.
Explicit 2
3 Select the All domains check box.
4 Locate the Output Entities section. From the Output entities list, choose Adjacent
boundaries.

114
6 In the Rename Explicit dialog box, type Exterior boundaries in the New label text
field.
7 Click OK.
Explicit 3
6 In the Rename Explicit dialog box, type Bulk electrolyte boundary in the New
label text field.
7 Click OK.
Explicit 4
4 Click Paste Selection.
5 In the Paste Selection dialog box, type 8, 13, 18, 25, 30 in the Selection text field.
6 Click OK.
8 In the Rename Explicit dialog box, type Cathode in the New label text field.
9 Click OK.
Adjacent 1
1 On the Definitions toolbar, click Adjacent.
2 In the Settings window for Adjacent, locate the Input Entities section.
3 Under Input selections, click Add.
4 In the Add dialog box, select Fixed domain in the Input selections list.
5 In the Input selections list, select Fixed domain.
6 Click OK.
7 Right-click Component 1 (comp1)>Definitions>Adjacent 1 and choose Rename.
8 In the Rename Adjacent dialog box, type Fixed boundaries in the New label text
field.

115
9 Click OK.
Difference 1
1 On the Definitions toolbar, click Difference.
2 In the Settings window for Difference, locate the Geometric Entity Level section.
3 From the Level list, choose Boundary.
4 Locate the Input Entities section. Under Selections to add, click Add.
5 In the Add dialog box, select Exterior boundaries in the Selections to add list.
6 In the Selections to add list, select Exterior boundaries.
7 Click OK.
8 In the Settings window for Difference, locate the Input Entities section.
9 Under Selections to subtract, click Add.
10 In the Add dialog box, In the Selections to subtract list, choose Cathode and Fixed
boundaries.
11 Click OK.
12 Right-click Component 1 (comp1)>Definitions>Difference 1 and choose Rename.
13 In the Rename Difference dialog box, type Photoresist vertical walls in the
14 Click OK.
ELECTRODEPOSITION, SECONDARY (EDSEC)
Electrolyte 1
Now start setting up the physics, begin with the current distribution model.
1 In the Settings window for Electrolyte, locate the Electrolyte section.

2 From the σl list, choose User defined. In the associated text field, type sigma.
Fixed Mesh 1
1 On the Physics toolbar, click Domains and choose Fixed Mesh.
2 In the Settings window for Fixed Mesh, locate the Domain Selection section.
3 From the Selection list, choose Fixed domain.
Electrolyte Potential 1
1 On the Physics toolbar, click Boundaries and choose Electrolyte Potential.

116
External Depositing Electrode 1

1 On the Physics toolbar, click Boundaries and choose External Depositing Electrode.
2 In the Settings window for External Depositing Electrode, locate the Boundary
Selection section.
3 From the Selection list, choose Cathode.
4 Locate the Boundary Condition section. From the Boundary condition list, choose
Average current density.
5 In the il,average text field, type i_avg.
1 In the Model Builder window, expand the External Depositing Electrode 1 node, then
click Electrode Reaction 1.
2 In the Settings window for Electrode Reaction, locate the Equilibrium Potential
section.
3 In the Eeq text field, type Eeq_Cu.
4 Locate the Electrode Kinetics section. From the Kinetics expression type list, choose
Concentration dependent kinetics.
5 In the i0 text field, type i0.
6 In the αa text field, type alpha_a.
7 In the αc text field, type alpha_c.
8 In the CO text field, type c/c_ref.
9 Locate the Stoichiometric Coefficients section. In the nm text field, type 2.
10 In the νcdep text field, type 1.
Nondepositing Boundary 1
Constrain the movement on the vertical walls of the photo resist and on the boundary
between the fixed and deforming domain by using the Zero normal displacement
setting. (This imposes a more stable constraint than the default Zero Normal Velocity
condition.)
1 In the Model Builder window, under Component 1 (comp1)>Electrodeposition,

Secondary (edsec) click Nondepositing Boundary 1.
2 In the Settings window for Nondepositing Boundary, locate the Nondepositing
Boundary section.
3 From the Boundary condition list, choose Zero normal displacement.

117
Nondepositing Boundary 2
1 On the Physics toolbar, click Boundaries and choose Nondepositing Boundary.
2 In the Settings window for Nondepositing Boundary, locate the Boundary Selection
section.
3 From the Selection list, choose Photoresist vertical walls.
4 Locate the Nondepositing Boundary section. From the Boundary condition list, choose
Zero normal displacement.
5 Select the Allow deformation along specified line only check box.
6 Specify the ldef vector as
0 x
0 y
1 z
Initial Values 1
1 In the Model Builder window, under Component 1 (comp1)>Electrodeposition,
Secondary (edsec) click Initial Values 1.
3 In the phil text field, type -Eeq_Cu.
On the Physics toolbar, click Electrodeposition, Secondary (edsec) and choose Transport
of Diluted Species (tds).
Now set up the model for the transport of copper ions in the electrolyte. The
electrolyte is assumed to be quiescent within the modeled diffusion layer.
1 In the Model Builder window, under Component 1 (comp1) click Transport of Diluted
Species (tds).
2 In the Settings window for Transport of Diluted Species, locate the Transport
Mechanisms section.
3 Clear the Convection check box.
Species (tds) click Transport Properties 1.
2 In the Settings window for Transport Properties, locate the Diffusion section.
3 In the Dc text field, type D_Cu.

118
Concentration 1
1 On the Physics toolbar, click Boundaries and choose Concentration.
2 In the Settings window for Concentration, locate the Boundary Selection section.
3 From the Selection list, choose Bulk electrolyte boundary.
4 Locate the Concentration section. Select the Species c check box.
5 In the c0,c text field, type c_ref.
Electrode-Electrolyte Interface Coupling 1

1 On the Physics toolbar, click Boundaries and choose Electrode-Electrolyte Interface
Coupling.
2 In the Settings window for Electrode-Electrolyte Interface Coupling, locate the
Reaction Coefficients 1
1 In the Model Builder window, expand the Electrode-Electrolyte Interface Coupling 1
node, then click Reaction Coefficients 1.
2 In the Settings window for Reaction Coefficients, locate the Model Inputs section.
3 From the iloc list, choose Local current density (edsec/ede1/er1).
4 Locate the Stoichiometric Coefficients section. In the nm text field, type 2.
5 In the νc text field, type -1.
Initial Values 1
Species (tds) click Initial Values 1.
3 In the c text field, type c_ref.
MESH 1
Build the mesh by sweeping from the cathode.
Size 1
1 In the Model Builder window, under Component 1 (comp1) right-click Mesh 1 and
choose Size.
2 In the Settings window for Size, locate the Geometric Entity Selection section.

119
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 text field, type a1/2.
Size 2
1 In the Model Builder window, right-click Mesh 1 and choose Size.
2 In the Settings window for Size, locate the Geometric Entity Selection section.
5 Locate the Element Size section. Click the Custom button.
6 Locate the Element Size Parameters section. Select the Maximum element growth rate
check box.
7 In the associated text field, type 1.2.
Mapped 1
1 Right-click Mesh 1 and choose More Operations>Mapped.
2 In the Settings window for Mapped, locate the Boundary Selection section.
4 In the Paste Selection dialog box, type 25 in the Selection text field.
5 Click OK.
6 In the Settings window for Mapped, click to expand the Advanced settings section.
7 Locate the Advanced Settings section. Select the Adjust evenly distributed edge mesh
check box.
8 Click the Build Selected button.
Free Triangular 1
1 Right-click Mesh 1 and choose More Operations>Free Triangular.
2 In the Settings window for Free Triangular, locate the Boundary Selection section.
4 In the Paste Selection dialog box, type 8, 13, 18, 30 in the Selection text field.
5 Click OK.
Swept 1
1 Right-click Mesh 1 and choose Swept.

120
2 In the Settings window for Swept, locate the Domain Selection section.
3 From the Geometric entity level list, choose Domain.
4 From the Selection list, choose Deforming domain.
5 Right-click Component 1 (comp1)>Mesh 1>Swept 1 and choose Distribution.
6 Right-click Swept 1 and choose Build Selected.
Free Triangular 2
1 Right-click Mesh 1 and choose More Operations>Free Triangular.
Swept 2
Right-click Mesh 1 and choose Swept.
Distribution 1
1 In the Model Builder window, under Component 1 (comp1)>Mesh 1 right-click Swept
2 and choose Distribution.
2 In the Settings window for Distribution, locate the Distribution section.
3 From the Distribution properties list, choose Predefined distribution type.
4 In the Element ratio text field, type 2.
STUDY 1
Step 2: Time Dependent

1 In the Model Builder window, under Study 1 click Step 2: Time Dependent.
2 In the Settings window for Time Dependent, locate the Study Settings section.
3 In the Times text field, type range(0,30,180).
This problem is fairly small, use a direct and fully coupled solver to reduce the
computation time.
Solution 1

121
3 Right-click Time-Dependent Solver 1 and choose Fully Coupled.

4 In the Settings window for Fully Coupled, click to expand the Method and
termination section.
5 Locate the General section. From the Linear solver list, choose Direct 1.
6 Locate the Method and Termination section. From the Nonlinear method list, choose
Automatic (Newton).
RESULTS
Data Sets
The following steps reproduce the figures from the Results and Discussion section of
the model documentation.
6 Click the Transparency button on the Graphics toolbar.
3D Plot Group 1
2 In the Settings window for 3D Plot Group, locate the Plot Settings section.
3 Clear the Plot data set edges check box.
4 Right-click Results>3D Plot Group 1 and choose Slice.
5 In the Settings window for Slice, click Replace Expression in the upper-right corner
of the Expression section. From the menu, choose Model>Component 1>Transport of
Diluted Species>c - Concentration.
6 Locate the Plane Data section. In the Planes text field, type 1.

122
the menu, choose Model>Component 1>Transport of Diluted Species>c -
Concentration.
12 Click to expand the Inherit style section. Locate the Inherit Style section. From the
Plot list, choose Slice 1.
14 Right-click 3D Plot Group 1 and choose Streamline.
15 In the Settings window for Streamline, click Replace Expression in the upper-right
corner of the Expression section. From the menu, choose Model>Component
1>Electrodeposition, Secondary>edsec.Ilx,...,edsec.Ilz - Electrolyte current density
vector (Material).
16 Locate the Streamline Positioning section. From the Positioning list, choose Start
point controlled.
17 From the Entry method list, choose Coordinates.
18 In the x text field, type 0.
19 In the y text field, type range(-150e-6,20e-6,150e-6).
20 In the z text field, type d_dl+d_pr.
21 Locate the Coloring and Style section. From the Line type list, choose Tube.
22 From the Color list, choose Black.
3D Plot Group 2
Change the frame of the data set edges to Geometry in order to show the outline
of the original (non-deformed) geometry in the figure.
3 From the Frame list, choose Geometry (Xg, Yg, Zg).
the menu, choose Model>Component 1>Electrodeposition, Secondary>Electrode
kinetics>edsec.iloc_er1 - Local current density.

123

3D Plot Group 3
1 In the Model Builder window, right-click 3D Plot Group 2 and choose Duplicate.
2 In the Model Builder window, expand the 3D Plot Group 3 node, then click Surface 1.
of the Expression section. From the menu, choose Model>Component
1>Electrodeposition, Secondary>edsec.sbtot - Total electrode thickness change.
4 Locate the Expression section. From the Unit list, choose μm.
8 From the Time (s) list, choose 0.
9 Locate the Expression section. In the Expression text field, type 1.
10 Locate the Coloring and Style section. From the Coloring list, choose Uniform.
11 From the Color list, choose Black.
Data Sets
1 On the Results toolbar, click Cut Plane.
2 In the Settings window for Cut Plane, locate the Plane Data section.
3 In the x-coordinate text field, type -1e-6.
2D Plot Group 4
3 From the Frame list, choose Geometry (Xg, Yg, Zg).

124
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Chemical Reaction Engineering

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COMSOL Multiphysics Training

Mass, Energy, and Momentum Transport

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Reaction Engineering Interface

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• Battery Interfaces (B&FC only)

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• Chemical Engineering Module

Density,viscosity reaction rate =f(c)

Convection and Conduction

⯜⒬⫵ 1 – One-way coupled

Energy : Convection and Conduction

Mass : Convection and Diffusion § E ·

⯜⒬⫵ 2 – Fully Coupled

Energy : Convection and Conduction

Mass : Convection and Diffusion § E ·

㫴ⵤ㐑㉘㥉 Model Navigator

Ɒ㉥ᵆ/᷸ᷱᵆ ㉘㥉 'omain / Boundary Settings

Density,viscosity reaction rate =f(c)

Convection and Conduction

< Constants > < THPS dependent >

< Constants > < THPS dependent >

< Constants > < THPS dependent >

The full 3D representation of the reactor geometry is given in Figure 1.

simulation (see Figure 2).

Inlet Heating cylinder Outlet

The reaction rate (SI unit: mol/(m3·s)) is given by:

where rate constant k (SI unit: s−1) is temperature–dependent according to the

In Equation 1, A is the frequency factor (1 × 1010 1/s), E the activation energy

where H is the heat of reaction (−100 kJ/mol).

and the momentum equations:

This is a useful boundary condition, particularly in convection-dominated energy

Equation 12 assumes that the species i is diluted in a solvent.

PREPARING FOR MODELING

PROPERTY AT 300 K AT 325 K

Density (kg/m3) 997 987

The Flow Regime

Calculating the Reynolds number at 325 K produces a nearly identical result.

Dilute or Concentrated Mixtures

In COMSOL Multiphysics, the Transport of Diluted Species interface is appropriate

As a rule of thumb, you can consider concentrations of up to 10 mol% of a solute in a

In the example at hand, the compound A is dissolved in water at a concentration of

Solving Coupled Models

Furthermore, the source term Ri in Equation 17 is a function of the temperature,

The last step leads to a fully coupled problem:

• The momentum transport depends on the energy transport.

Results and Discussion

Figure 3: Velocity field (m/s) in the reactor.

Figure 5: Concentration of the heat sensitive chemical (A) (mol/m3) as function of

Application Library path: Chemical_Reaction_Engineering_Module/

4 Locate the Position section. In the x text field, type xpos.

7 Select Boundary 1 only.

LAMINAR FLOW (SPF)

3 From the Selection list, choose Outlet.

5 Click Add to Component in the window toolbar.

1 On the Physics toolbar, click Multiphysics and choose Global>Flow Coupling.

Mass : Convection and Diffusion § E ·

Mass : Convection and Diffusion § E ·