Electrochemistry Module: Application Library Manual

Electrochemistry Module
Application Library Manual

Electrochemistry Module Application Library Manual
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Part number: CM024303

Created in COMSOL Multiphysics 5.3a
Current Distribution in a Chlor-Alkali Membrane

Cell
This model is licensed under the COMSOL Software License Agreement 5.3a.
All trademarks are the property of their respective owners. See www.comsol.com/trademarks.
Introduction
The chlor-alkali membrane process is one of the largest processes in industrial electrolysis
with production of roughly 40 million metric tons of both chlorine and caustic soda per
year (Ref. 1). Chlorine’s largest use is in the production of vinyl chloride monomer, which
in turn is used for the production of polyvinyl chloride (PVC). Among the applications of
PVC are as electrical insulator in cables and as a material for pipes, carpets, raincoats, and
many other products. The production of chlorine implies a simultaneous production of
caustic soda (alkali), which is widely used in the chemical industry for alkalization and
neutralization of acidic streams. Caustic soda is also used in alkaline batteries.
The traditional process for manufacturing chlorine and caustic soda is the mercury-cell
process. This technology has been partly replaced by the diaphragm process, and in later
years the membrane process has been the dominating process in retrofits and for new
plants. The purpose of the diaphragm or membrane is to separate the products chlorine
and caustic soda, which otherwise would react to produce hypochlorite and hydrochloric
acid. Chlorine and caustic soda are produced at the anode and cathode, respectively.
Figure 1 shows a diagram of the process.
Current density in membrane-cell technology has increased dramatically during the last
decade as the membranes themselves have improved. This results in lower investment costs
for greater production. However, the increase in current density implies an increase in
power consumption if nothing is done to dampen the voltage increase. Advances in cell
design by increased internal convection, decreased ohmic losses, and better membranes
have allowed for large increases in current density with small increases in cell voltage. One
of the important parameters in the design of modern membrane cells is the current-density
distribution on the electrode surfaces. It is important, from the viewpoint of catalyst
lifetime and minimization of losses, that the current density on the electrode frontal
surfaces is as uniform as possible.
This example describes the current-density distribution in a realistic structure for the
anodes and cathodes in a membrane cell. This discussion limits the model to one unit cell
of the entire cell. This unit cell appears on the right side in Figure 1.
2 | C U R R E N T D I S T R I B U T I O N I N A C H L O R- A L K A L I M E M B R A N E C E L L
Outlet caustic Membrane
H2
Cathode
Outlet brine
Cl2
Cathode
compartment
Anode
compartment
Inlet brine Anode
Inlet caustic
Figure 1: Drawing of the unit cell.
The anode and cathode ribs are separated by the membrane, which is a cation-selective
membrane. It is forced to adapt its shape to fit within the inter-electrode distance. The
membrane prevents mixing between brine and chlorine on the anode side with the caustic
soda and hydrogen on the cathode side.
A detailed description of the process of chlor-alkali electrolysis is available in Ref. 1.
Model Definition
This example models the current and potential distribution in a unit cell in the membrane
cell sketched in Figure 1. This model is a secondary current-distribution model (see
Ref. 2), which implies that you take into account the dependence of the electron transfer
on the local potential, and that you assume constant composition in the subdomains. The
electron transfer reactions at the anode and cathode surfaces are:
- -
2Cl ⇔ Cl 2 (g) + 2e at the anode
- -
2H 2 O + 2e ⇔ H 2 (g) + 2OH at the cathode
The domain in the model is half of the unit cell shown in Figure 1, as explained in
Figure 2.
Catholyte
Cathode
Anode Membrane
Anolyte
Figure 2: Model geometry.
The chemical reactions show that there is gas evolution in both the anodic and cathodic
compartments, creating a vigorous internal convection in the respective compartments.
This makes it possible to simplify the model by neglecting the concentration gradients in
the anolyte and catholyte. The simplification implies that the transport of ionic current
inside the cell takes place exclusively through migration, that is, the electric field induces
a flux of ions. For this reason you do not need to model the complex problem of internal
free convection of the two-phase flow in order to get an estimation of the current-density
distribution in the cell (see also the theory for the Current Distribution interfaces in the
Electrochemistry Module User’s Guide).
Model the current conduction in the membrane and two electrolyte chambers by using
the Secondary Current Distribution interface, with different values for the electrolyte
conductivity in each domain.
The anode reaction is very fast, and small changes in potential provide large changes in
current density. This implies that you can negligible a over potential (primary condition)
at the anode’s surface:
E eq, a = φ s, a – φ l, c (1)
In this case this gives an error in potential of approximately 20 mV at that surface (Ref. 3).
The cell voltage, Ecell, can be written as the difference in metal potential between the
anode and cathode:
E cell = φ s, a – φ s, c (2)
The cell potential may also be expressed based on the equilibrium potentials and the cell
polarization potential as:
E cell = E eq, a – E eq, c + E pol (3)
which results in
φ s, c = φ s, a – ( E eq, a – E eq, c + E pol ) (4)
Grounding the electrolyte potential at the anode, φl,a we get:
φ l, a = 0 (5)
which is used as a boundary condition for the anode boundary.
In combination with the primary condition above this results in
φ s, c = – ( – E eq, c + E pol ) (6)
Using the cathode as reference potential (Eeq,c=0) when defining the kinetics this results
in
φ s, c = – E pol (7)
This potential is used when defining the Butler-Volmer expression for the relation between
current density and potential on the cathode electrode boundary.
Results and Discussion

Figure 3 shows the potential in the anode and cathode compartments as well as in the
membrane electrolyte. From this plot note that the largest ohmic losses arise in the
membrane, as expected from its low conductivity. The arrow plot of the current-density
vector shows how the distribution is more uniform on the cathode than on the anode
surface.
Figure 3: Electrolyte potential.
Figure 4: Electrolyte current density magnitude.
Figure 4 shows the modulus of the current-density vector, which illustrates “hot spots” in
the electrolyte where the current density is large. On the parts of the electrodes where the
current density is high, catalyst can be lost due to accelerated wear.
References
1. H.S. Burney, “Past Present and Future of the Chlor-Alkali Industry,” Chlor-Alkali and
Chlorate Technology: R.B. Macmullin Memorial Symposium, Proc Electrochemical
Society, vol. 99–21, 1999.
2. J.S. Newman, Electrochemical Systems, 2nd ed., Prentice Hall, 1991.
3. P. Bosander, P. Byrne, E. Fontes, and O. Parhammar, Current Distribution on a

Membrane Cell Anode, Chlor-Alkali and Chlorate Technology: R.B. Macmullin
Memorial Symposium, Proc Electrochemical Society, vol. 99-21, 1999.
Application Library path: Electrochemistry_Module/

Electrochemical_Engineering/chlor_alkali
Modeling Instructions
From the File menu, choose New.
NEW
In the New window, click Model Wizard.
MODEL WIZARD
1 In the Model Wizard window, click 2D.
2 In the Select Physics tree, select Electrochemistry>
Primary and Secondary Current Distribution>Secondary Current Distribution (cd).
3 Click Add.
4 Click Study.
5 In the Select Study tree, select Preset Studies>Stationary.
6 Click Done.
GLOBAL DEFINITIONS
Start by loading the model parameters from a text file.
Parameters
1 In the Model Builder window, under Global Definitions click Parameters.
2 In the Settings window for Parameters, locate the Parameters section.
3 Click Load from File.
4 Browse to the model’s Application Libraries folder and double-click the file
chlor_alkali_parameters.txt.
GEOMETRY 1
The model geometry is available as a parameterized geometry sequence in a separate
MPH-file. If you want to build it from scratch, follow the instructions in the section
Appendix — Geometry Modeling Instructions. Otherwise load it from file with the
following steps.
1 On the Geometry toolbar, click Insert Sequence.

chlor_alkali_geom_sequence.mph.
3 On the Geometry toolbar, click Build All.

4 Click the Zoom Extents button on the Graphics toolbar.
MATERIALS
Define the electrolyte conductivity in the three different domains by adding separate
materials for the catholyte, the membrane and the anolyte.
Material 1 (mat1)
1 In the Model Builder window, under Component 1 (comp1) right-click Materials and
choose Blank Material.
2 In the Settings window for Material, locate the Geometric Entity Selection section.
3 Click Clear Selection.
4 Select Domain 3 only.
5 Locate the Material Contents section. In the table, enter the following settings:
Property Variable Value Unit Property group

Electrolyte conductivity sigmal K_c S/m Electrolyte conductivity
Material 2 (mat2)
1 Right-click Materials and choose Blank Material.
3 In the Settings window for Material, locate the Material Contents section.
4 In the table, enter the following settings:

Electrolyte conductivity sigmal K_m S/m Electrolyte conductivity
Material 3 (mat3)
1 Right-click Materials and choose Blank Material.

Electrolyte conductivity sigmal K_a S/m Electrolyte conductivity
SECONDARY CURRENT DISTRIBUTION (CD)

Set up the cathode current density by using an Electrode Surface node. Define the
exchange current density in the Electrode Reaction child node.
Electrode Surface 1
1 On the Physics toolbar, click Boundaries and choose Electrode Surface.
2 Select Boundaries 10–12 and 22 only.
3 In the Settings window for Electrode Surface, locate the Boundary Condition section.
4 In the φs, ext text field, type -E_pol.
Electrode Reaction 1
1 In the Model Builder window, expand the Electrode Surface 1 node, then click
Electrode Reaction 1.
2 In the Settings window for Electrode Reaction, locate the Model Input section.
3 In the T text field, type T.
4 Locate the Electrode Kinetics section. From the Kinetics expression type list, choose
Butler-Volmer.
5 In the i0 text field, type i0_c.
Electrolyte Potential 1
Assuming fast reaction kinetics, a constant potential is set at the anode surface.
Define the potential on the anode by using an Electrolyte Potential node.
1 On the Physics toolbar, click Boundaries and choose Electrolyte Potential.
2 Select Boundaries 3, 8, 9, and 17 only.
MESH 1
Create a triangular mesh with a higher resolution at the electrode surfaces and on the
membrane boundaries.
Size 1
1 In the Model Builder window, under Component 1 (comp1) right-click Mesh 1 and choose
Free Triangular.
2 Right-click Free Triangular 1 and choose Size.
3 In the Settings window for Size, locate the Geometric Entity Selection section.
4 From the Geometric entity level list, choose Boundary.
Select the anode, cathode and membrane boundaries. The easiest way to do this is by
using a selection box around the central part of the geometry.
5 Click the Select Box button on the Graphics toolbar.
6 Select Boundaries 3–5, 8–12, 14, 15, and 17–22 only.
7 Locate the Element Size section. From the Predefined list, choose Extremely fine.
8 In the Model Builder window, click Mesh 1.
9 In the Settings window for Mesh, click Build All.
Free Triangular 1
The finalized mesh should now look like this:
1 In the Settings window for Free Triangular, click Build All.
STUDY 1
The problem is now ready for solving.
1 On the Home toolbar, click Compute.
RESULTS
Electrolyte Potential (cd)

The first default plot shows the electrolyte potential and an an arrow plot of the electrolyte
currents.
Electrolyte Current Density (cd)

The second default plot visualizes the electrolyte current density.
1 In the Model Builder window, under Results click Electrolyte Current Density (cd).
2 On the Electrolyte Current Density (cd) toolbar, click Plot.
Appendix — Geometry Modeling Instructions

NEW
In the New window, click Blank Model.
ROOT
On the Home toolbar, click Component and choose Add Component>2D.
GEOMETRY 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)
1 On the Geometry toolbar, click Primitives and choose Rectangle.
2 In the Settings window for Rectangle, locate the Size and Shape section.
3 In the Width text field, type 3.5.
4 In the Height text field, type 10.
5 Locate the Position section. In the x text field, type -3.5.
6 In the y text field, type -4.
Bézier Polygon 1 (b1)

1 On the Geometry toolbar, click Primitives and choose Bézier Polygon.
2 In the Settings window for Bézier Polygon, locate the Polygon Segments section.
3 Find the Added segments subsection. Click Add Linear.
4 Find the Control points subsection. In row 1, set x to -3.5.
5 In row 1, set y to 0.3.
6 In row 2, set x to -2.25.
7 In row 2, set y to -0.3.
12 Find the Control points subsection. In row 2, set y to 1.5.
14 Find the Added segments subsection. Click Add Quadratic.
15 Find the Control points subsection. In row 2, set x to -3.
Bézier Polygon 2 (b2)

1 On the Geometry toolbar, click Primitives and choose Bézier Polygon.
2 In the Settings window for Bézier Polygon, locate the Polygon Segments section.
11 Find the Control points subsection. In row 2, set y to 2.
14 In row 3, set x to -1.75.
Rotate 1 (rot1)
1 On the Geometry toolbar, click Transforms and choose Rotate.
2 Select the objects b2 and b1 only.
3 In the Settings window for Rotate, locate the Input section.
4 Select the Keep input objects check box.
5 Locate the Rotation Angle section. In the Rotation text field, type 180.
6 Locate the Center of Rotation section. In the x text field, type -1.75.
7 In the y text field, type 1.55.
Union 1 (uni1)
1 On the Geometry toolbar, click Booleans and Partitions and choose Union.
2 Select the objects b2 and rot1(2) only.
3 In the Settings window for Union, locate the Union section.
4 Clear the Keep interior boundaries check box.
Difference 1 (dif1)
1 On the Geometry toolbar, click Booleans and Partitions and choose Difference.
2 Select the object r1 only.
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 rot1(1) and b1 only.
Cyclic Voltammetry at a Macroelectrode in 1D
Introduction
Cyclic voltammetry is a common analytical technique for investigating electrochemical
systems. In this method, the potential difference between a working electrode and a
reference electrode is swept linearly in time from a start potential to a vertex potential, and
back again (see Figure 1). The resulting current at the working electrode is recorded and
is plotted against the applied electrode potential in a voltammogram.
Figure 1: Potential of the working electrode during one voltammetric cycle. The potential is
cycled between the vertex potentials 0.4 V and –0.4 V. The scan rate is 1 mV/s.
Voltammetry is a valuable technique because information about both the electrochemical

reactivity and the transport properties of a system can be extracted simultaneously. For
quantitative interpretation of voltammetry, however, we must use numerical methods to
solve the physical equations that describe voltammetry. Then, unknown physical quantities
in the system can be inferred by ‘fitting’ to experimental data.
This example demonstrates the use of a common approximation in which a large electrode
(macroelectrode) is assumed to have uniform transport behavior across its surface, so only
physics occurring normal to the surface need to be considered. By simplifying the model
to 1D, an efficient time-dependent analysis is possible.
In this model, a Parametric Sweep is used to compare voltammetry recorded at different

voltammetric scan rates.
2 | C Y C L I C VO L T A M M E T R Y A T A M A C R O E L E C T R O D E I N 1 D
Model Definition
The model contains a single 1D domain of length L, which is the maximum extent of the
diffusion layer over the duration of the voltammetry experiment. A conservative setting for
L is set to greatly exceed the mean diffusion layer thickness:
L = 6 Dt max
Here, D is the diffusion coefficient of the reactant and tmax is the duration of the cyclic
voltammogram.
D O M A I N E Q UAT I O N S
We assume the presence of a large quantity of supporting electrolyte. This is inert salt that
is added in electroanalytical experiments to increase the conductivity of the electrolyte
without otherwise interfering with the reaction chemistry. Under these conditions, the
resistance of the solution is sufficiently low that the electric field is negligible, and we can
assume φl = 0.
The Electroanalysis interface implements chemical transport equations for the reactant and
product species of the redox couple subject to this assumption. The domain equation is
the diffusion equation (also known as Fick’s 2nd law) to describe the chemical transport
of the electroactive species A and B:
∂c i
------- = ∇ ⋅ ( D i ∇c i )
∂t
B OU N DA RY EQ UAT IO N S
At the bulk boundary (x = L), we assume a uniform concentration equal to the bulk
concentration for the reactant. The product has zero concentration here, as in bulk.
At the electrode boundary (x = 0), the reactant species A oxidizes (loses one electron) to
form the product B. By convention, electrochemical reactions are written in the reductive
direction:
–
B+e ↔A
The stoichiometric coefficient is –1 for B, the “reactant” in the reductive direction, and +
1 for A, the “product” in the reductive direction. This formulation is consistent even in
examples such as this model where at certain applied potentials, the reaction proceeds
favorably to convert A to B. The number of electrons transferred, n, equals one.
The current density for this reaction is given by the electroanalytical Butler-Volmer
equation for an oxidation:
( n – α c )Fη – α c Fη
i loc = nFk 0  c A exp  ---------------------------- – c B exp  ----------------- 
RT RT
in which k0 is the heterogeneous rate constant of the reaction, αc is the cathodic transfer
coefficient, and η is the overpotential at the working electrode. This overpotential is the
difference between the applied potential and the equilibrium potential (formal reduction
potential) of the redox couple of species A and B.
According to Faraday’s laws of electrolysis, the flux of the reactant and product species are
proportional to the current density drawn:
ν i i loc
– n ⋅ N i = -------------
nF
This is expressed in the Electrode Surface boundary condition.
The applied triangular waveform for the cyclic voltammetry study is specified in the
Electrode Surface boundary condition according to two vertex potentials—forming a
potential window between –0.4 V and +0.4 V, either side of the equilibrium reduction
potential—and a voltammetric scan rate, v (SI unit: V/s), which is the rate at which the
applied potential is changed.
In the 1D approximation, the total current is related to the current density simply by
multiplying by the electrode area A:
I el = i loc A
C Y C L I C V O LTA M M E T RY S T U DY
In the cyclic voltammetry experiment, the potential applied to the working electrode
surface is varied linearly as a function of time. A Parametric Sweep is used to compare the
voltammetry recorded at different scan rates.
The shape of the cyclic voltammogram (Figure 2) shows the relation between electrode
kinetics and chemical species transport (diffusion).
Figure 2: Cyclic voltammetry recorded at a macroelectrode.
Initially, at reducing potentials, the oxidation reaction is not driven and negligible current
is drawn. As the potential moves towards the reduction potential of the redox couple, the
oxidation reaction is accelerated and the current increases. Once the oxidation reaction has
consumed the reactant at the electrode surface, the current becomes limited by the rate of
transport of A towards the working electrode. Therefore, a peak current is observed, and
at higher potentials, the voltammetric current falls off at a potential-independent rate; this
region is termed “diffusion-controlled” or “transport-controlled”.
On sweeping back towards more reducing potentials, the reconversion of the product B
into the original reactant A gives a negative (cathodic, reductive) current. Depletion of the
reacting species B causes a negative peak current and reconversion thereafter proceeds at
a diffusion-controlled rate.
The magnitude of the current on the forward peak, Ipf, is a common diagnostic variable
in voltammetry. For fast electrode kinetics and at a macroelectrode under the 1D
approximation, its value is given theoretically by the Randles–Ševcík equation (see Ref. 1
and Ref. 2 for a detailed discussion and derivation):
nF
I pf = 0,446nFAc -------- Dv
RT
where A is the electrode area, c is the bulk concentration of the reactant, and D is the
diffusion coefficient of the reactant.
The square-root relationship between peak current and scan rate is characteristic of
macroelectrode cyclic voltammetry under the above conditions.
References
1. R.G. Compton and C.E. Banks, Understanding Voltammetry, 2nd ed., London,
2011.
2. A.J. Bard and L.R. Faulkner, Electrochemical Methods, Fundamentals and

Applications, 2nd ed., Wiley, New York, 2001.
Application Library path: Electrochemistry_Module/Tutorials/

cyclic_voltammetry_1d
NEW
MODEL WIZARD
2 In the Select Physics tree, select Electrochemistry>Electroanalysis (elan).
3 Click Add.
This model will solve for the two concentrations of a redox couple, change the default
concentration variable names to cA and cB.
4 In the Concentrations table, enter the following settings:
cA
cB
5 Click Study.
6 In the Select Study tree, select Preset Studies>Cyclic Voltammetry.
7 Click Done.
GLOBAL DEFINITIONS
Parameters
Add the model parameters from a text file.

cyclic_voltammetry_1d_parameters.txt.
GEOMETRY 1
Build the model geometry as a single interval, where the left boundary will later be defined
as the electrode surface, and the right boundary will be the boundary towards the bulk.
Interval 1 (i1)
1 On the Geometry toolbar, click Interval.
Set the interval length to L. The value of L is defined in the Parameters node. Note that
L will vary with the Voltammetric scan rate parameter v, which is also defined in the
Parameters node.
2 In the Settings window for Interval, locate the Interval section.
3 In the Right endpoint text field, type L.
The completed geometry should now look like this:
ELECTROANALYSIS (ELAN)
Transport Properties 1
Start defining the physics by setting the diffusion coefficients for the two species of the
redox couple.
1 In the Model Builder window, under Component 1 (comp1)>Electroanalysis (elan) click

Transport Properties 1.
2 In the Settings window for Transport Properties, locate the Diffusion section.
3 In the DcA text field, type DA.
4 In the DcB text field, type DB.
Concentration 1
Set the boundary to the right to bulk concentration values.
1 On the Physics toolbar, click Boundaries and choose Concentration.

2 Select Boundary 2 only.
3 In the Settings window for Concentration, locate the Concentration section.
4 Select the Species cA check box.
5 In the c0,cA text field, type c_bulk.
6 Select the Species cB check box.
Electrode Surface 1
Set up the electrode surface and the cyclic voltammetry settings on the left boundary.

4 From the Boundary condition list, choose Cyclic voltammetry.
5 In the Linear sweep rate text field, type v.
The voltage will be cycled between the vertex potentials. When the start potential is not
specified, the sweep will start at Vertex potential 2.
6 In the Vertex potential 1 text field, type E_vertex1.
7 In the Vertex potential 2 text field, type E_vertex2.
Specify the electrode reaction as an Electroanalytical Butler-Volmer reaction, which is
concentration dependent as defined by the stoichiometric coefficients.
4 Locate the Electrode Kinetics section. In the k0 text field, type k0.
5 Locate the Stoichiometric Coefficients section. In the νcA text field, type 1.
6 In the νcB text field, type -1.
Double Layer Capacitance 1

1 In the Model Builder window, under Component 1 (comp1)>Electroanalysis (elan) right-
click Electrode Surface 1 and choose Double Layer Capacitance.
2 In the Settings window for Double Layer Capacitance, locate the Double Layer Capacitance
section.
3 In the Cdl text field, type Cdl.
Initial Values 1
Specify the initial concentration values. This will set the concentration values when the
simulation starts at t = 0.
Initial Values 1.
2 In the Settings window for Initial Values, locate the Initial Values section.
3 In the cA text field, type c_bulk-cB0*(1-x/L).
4 In the cB text field, type cB0*(1-x/L).
STUDY 1
Solve the problem for various sweep rates.
Parametric Sweep
1 On the Study toolbar, click Parametric Sweep.
2 In the Settings window for Parametric Sweep, locate the Study Settings section.
3 Click Add.
Parameter name Parameter value list Parameter unit

v (Voltammetric scan rate) 10^range(-3,1,0) V/s
5 On the Study toolbar, click Compute.
RESULTS
Cyclic Voltammograms (elan)

A number of plots are created by default. The first default plot shows the voltammograms
created by the Cyclic Voltammetry feature in the Electrode Surface node.
1 In the Model Builder window, under Results click Cyclic Voltammograms (elan).
2 In the Settings window for 1D Plot Group, click to expand the Legend section.
3 From the Position list, choose Upper left.
Global 1
1 In the Model Builder window, expand the Cyclic Voltammograms (elan) node, then click
Global 1.
2 In the Settings window for Global, click to expand the Legends section.
3 Find the Include subsection. Clear the Description check box.
4 On the Cyclic Voltammograms (elan) toolbar, click Plot.
Diffuse Double Layer
Introduction
Close to an electrode surface, ions in the electrolyte are attracted and repelled by
unscreened excess charge on the electrode. This region is called the diffuse double layer.
Its size is normally a few nanometers away from the electrode surface. The electrical
interactions here mean that charge separation can occur, and the assumption of local
electroneutrality is not valid. The study of the diffuse double layer is important to
applications that consider very thin layers of electrolyte, such as electrochemical capacitors,
atmospheric corrosion problems, ion-selective field effect transistors (ISFETs), and
nanoelectrochemistry.
This example shows how to define a double layer model by combining the Transport of
Diluted Species and Electrostatics physics to account for mass transfer and charge transfer
respectively. The model contains one charged electrode adjacent to bulk solution. See also
the Diffuse Double Layer with Charge Transfer for a more sophisticated example with two
electrodes and electrochemical reactions.
One of the simplest physical models of the double layer is the Gouy-Chapman-Stern
(GCS) model. In Gouy-Chapman theory (Ref. 1, Ref. 2), the diffuse double layer is
treated as a multiphysics coupling of the Nernst-Planck equations for mass transport of all
of the ions, with the Poisson equation (Gauss’s law) for the charge density and electric
field. The combination of these equations is frequently referred to as the Poisson-Nernst-
Planck (PNP) equations or Nernst-Planck-Poisson (NPP) equations.
Gouy-Chapman theory predicts the spatial extent of the diffuse double layer to be of the
same order as the Debye length for the solution, defined for a monovalent binary
electrolyte with concentration cbulk and solvent relative permittivity εr:
RTε r ε 0
xD = ---------------------
- (1)
2
2F c bulk
The Stern modification (Ref. 3) to the Gouy-Chapman theory additionally considers the
electric field inside a plane called the outer Helmholtz plane (OHP). This is the plane of
closest approach to the electrode for dissolved ions in solution, due to the finite size of the
ions and surrounding solvent molecules. In the distance of a fraction of a nanometer
between this plane and the electrode surface, Stern’s theory describes the electrolyte as a
dielectric of constant permittivity. This uncharged region of the double layer is sometimes
called the compact double layer.
When there is a low applied potential (< RT/F ~ 25 mV), the Gouy-Chapman-Stern
theory has an analytical solution. The capacitance is predicted to be the same as for a
2 | DIFFUSE DOUBLE LAYER

parallel plate capacitor whose electrode separation is equal to the sum of the Stern layer
size and the Debye length:
εr ε0
C dl ≈ ------------------- (2)
xD + xS
Model Definition
The model geometry is in 1D (a single interval between 0 and L) and consists of a single
domain, representing the electrolyte phase from the electrode through the diffuse double
layer, as far as the electroneutral bulk solution. The compact component of the double
layer is handled using a boundary condition set at x = 0.
DOMAIN EQUATIONS
The concentrations, ci (SI unit: mol/m3, i=+,-), of two ions of opposite charge (+1/-1)
are solved for in the electrolyte phase. The fluxes (Ni, SI unit: mol/(m2·s)) of the ions are
described by the Nernst-Planck equation
N i = – D i ∇c i – u m, i z i Fc i ∇φ
with Di (SI unit: m2/s) being the diffusion coefficient, um,i (SI unit: s·mol/kg) the
mobility, F (SI unit: C/mol) the Faraday constant, and φ (SI unit: V) the electric potential
in the electrolyte phase.
We assume no homogeneous reactions of the ions in solution. Then, conservation of mass

requires that, for both species:
∇ ⋅ Ni = 0
For the potential, the Poisson equation (Gauss’s law) states
∇ ⋅ ( – ε∇φ ) = ρ
where ε is the permittivity (SI unit: F/m) and ρ the charge density (SI unit: C/m3). The
charge density depends on the ion concentrations according to:
ρ = F ( c+ – c- )
BOUNDARY CONDITIONS
We choose the bulk solution as the ground condition for the electrolyte potential:
φ = 0

which is set at the outer boundary.
The ion concentrations are set to their bulk values at the outer boundary. Because bulk
solution is electroneutral, the positive and negative ions have equal concentrations here.
From Gauss’s law, the electric field inside the compact double layer is constant because this
layer is uncharged and has a uniform permittivity. Hence, according to the Stern theory
for a compact double layer of a constant thickness, λS (SI unit: m), the following Robin-
type boundary condition applies for the electrolyte potential:
φ + λ S ( n ⋅ ∇φ ) = φ M
where φ M (SI unit: V) is the applied potential of the electrode, as measured against bulk
solution.
For the case of a non-zero Stern layer thickness, the condition can be reformulated as a
surface charge condition that depends on the potential difference, φ Δ (SI unit: V),
between the electrode potential and the electrolyte potential at the outer Helmholtz plane
(x = 0):
εφ Δ
n ⋅ ( – ε∇φ ) = – ---------
λS
where
φΔ = φM – φ
The Surface Charge Density condition in Electrostatics is used to define the above condition.
The problem is solved for a sweep of values of φ M from 1 mV to 10 mV.
If the electrode is inert to electrolysis of the ions at the electrolyte-electrode interface, no

flux of the ions into the electrode surface can occur. Hence, No Flux conditions are used
for both ion concentrations at the electrode boundary.

Figure 1 shows the potential profile in the electrolyte as a line graph and the potential at
the electrode as a point.
Figure 1: Electrolyte potential profile (blue line) and 10 mV applied electrode potential vs bulk
solution (red dot).
The potential difference between the red dot (electrode surface) and the value of the blue
line at x = 0 represents the potential difference over the compact double layer. The
electrolyte potential falls off exponentially on the Debye length scale (Equation 1), as
predicted by Gouy-Chapman theory.
Figure 2 shows the concentrations of the two ionic species. Because the electrode is
polarized positively against bulk solution, it is positively charged and attracts anions while
repelling cations. The concentration profiles confirm that the anion in the electrolyte is
accumulated at the surface, while the cation is depleted.

Figure 2: Concentration profile for the two ions, showing cation depletion (blue line) and
anion accumulation (green line).
Figure 3 shows the surface charge dependence on the applied potential. This agrees
precisely with the low potential analytical expression (Equation 2) for the smaller
potentials. At 10 mV applied potential, a small deviation is observed as the low potential
approximation becomes less precise.

Figure 3: Surface charge density as a function of applied potential difference between the
electrode and bulk solution, comparing simulation results with analytical theory derived in
the limit of low applied potential.
References
1. L.G. Gouy, Comptes Rendues Hebdomadaires des Séances de l’Académie des Sciences,
vol. 149, pp. 654-657, 1909.
2. D.L. Chapman, Philosophical Magazine, vol. 25, pp. 475-481, 1913.
3. O. Stern, Zeitschrift für Elektrochemie, vol. 30, pp. 508-516, 1924.
4. A.J. Bard and L.R. Faulkner, Electrochemical Methods: Fundamentals and

Applications, 2nd ed., Hoboken, 2001.
Application Library path: Electrochemistry_Module/Tutorials/

diffuse_double_layer

NEW
MODEL WIZARD
2 In the Select Physics tree, select Chemical Species Transport>Nernst-Planck-
Poisson Equations.
3 Click Add.
4 In the Electric potential text field, type phi.
5 In the Added physics interfaces tree, select Transport of Diluted Species (tds).
6 In the Number of species text field, type 2.
cA
cX
8 Click Study.
9 In the Select Study tree, select Preset Studies for Selected Physics Interfaces>Stationary.
10 Click Done.
GLOBAL DEFINITIONS
Start by loading some parameters from a text file.
Parameters
diffuse_double_layer_parameters.txt.
DEFINITIONS
Proceed by adding some variable expressions from a text file.

Variables 1
1 In the Model Builder window, under Component 1 (comp1) right-click Definitions and
choose Variables.
2 In the Settings window for Variables, locate the Variables section.
diffuse_double_layer_variables.txt.
GEOMETRY 1
Build the geometry as a single interval.
Interval 1 (i1)
3 In the Right endpoint text field, type L_cell.
4 Click Build All Objects.
ELECTROSTATICS (ES)
Charge Conservation 1
Now start setting up the physics, begin with the Electrostatics physics (Poisson’s
equation).
1 In the Model Builder window, under Component 1 (comp1)>Electrostatics (es) click

Charge Conservation 1.
2 In the Settings window for Charge Conservation, locate the Electric Field section.
3 From the εr list, choose User defined. In the associated text field, type eps_H2O.
Surface Charge Density 1

1 On the Physics toolbar, click Boundaries and choose Surface Charge Density.
3 In the Settings window for Surface Charge Density, locate the Surface Charge Density
section.
4 In the ρs text field, type rho_surf.
Ground 1
1 On the Physics toolbar, click Boundaries and choose Ground.

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 )
Now set up the model for the transport of the ions.
1 In the Model Builder window, under Component 1 (comp1)>
Transport of Diluted Species (tds) click Transport Properties 1.
2 In the Settings window for Transport Properties, locate the Model Input section.
3 In the T text field, type T0.
4 Locate the Diffusion section. In the DcA text field, type DA.
5 In the DcX text field, type DX.
6 Locate the Migration in Electric Field section. In the zcA text field, type zA.
7 In the zcX text field, type zX.
Initial Values 1
Transport of Diluted Species (tds) click Initial Values 1.
3 In the cA text field, type cA_bulk.
4 In the cX text field, type cX_bulk.
5 In the Model Builder window, click Transport of Diluted Species (tds).
Concentration 1
4 Select the Species cA check box.
5 In the c0,cA text field, type cA_bulk.
6 Select the Species cX check box.
7 In the c0,cX text field, type cX_bulk.
MESH 1
Edit the default meshing sequence, the mesh parameters are dependent of the Debye
length to make sure the mesh is always a well resolved.
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 Sequence type list, choose User-controlled mesh.
Size 1
1 In the Model Builder window, under Component 1 (comp1)>Mesh 1 right-click Edge 1 and
choose Size.
2 In the Settings window for Size, locate the Element Size section.
3 Click the Custom button.
4 Locate the Element Size Parameters section. Select the Maximum element size check box.
5 In the associated text field, type h_max.
Size 2
1 Right-click Edge 1 and choose Size.
5 Locate the Element Size section. Click the Custom button.
7 In the associated text field, type h_max_surf.
8 Click Build All.
STUDY 1
Step 1: Stationary
Solve the problem using an Auxiliary sweep for a range of potentials.
1 In the Settings window for Stationary, click to expand the Study extensions section.
2 Locate the Study Extensions section. Select the Auxiliary sweep check box.
3 Click Add.

phiM (Voltage of electrode vs range(1,1,10) mV
PZC)

RESULTS
Electric Potential (es)

Reproduce the figures from the Results and Discussion section as follows:
1 In the Model Builder window, under Results click Electric Potential (es).
2 In the Settings window for 1D Plot Group, locate the Data section.
3 From the Parameter selection (phiM) list, choose Last.
4 Locate the Plot Settings section. Select the y-axis label check box.
Line Graph 1
1 In the Model Builder window, expand the Electric Potential (es) node, then click
Line Graph 1.
2 In the Settings window for Line Graph, locate the x-Axis Data section.
3 From the Parameter list, choose Expression.
4 In the Expression text field, type x/xD.
5 Select the Description check box.
6 In the associated text field, type Length (unit Debye lengths).
Point Graph 1
1 In the Model Builder window, under Results right-click Electric Potential (es) and choose
Point Graph.
4 In the Settings window for Point Graph, locate the y-Axis Data section.
5 In the Expression text field, type phiM.
6 Locate the x-Axis Data section. From the Parameter list, choose Expression.
7 In the Expression text field, type x/xD.
8 Select the Description check box.
9 In the associated text field, type Length (unit Debye lengths).
10 Click to expand the Coloring and style section. Locate the Coloring and Style section.
Find the Line style subsection. From the Line list, choose None.
11 From the Color list, choose Red.
12 Find the Line markers subsection. From the Marker list, choose Point.
13 From the Positioning list, choose In data points.

14 On the Electric Potential (es) toolbar, click Plot.
Concentration (tds)
1 In the Model Builder window, under Results click Concentration (tds).
3 From the Parameter selection (phiM) list, choose Last.
4 Click to expand the Title section. From the Title type list, choose None.
Line Graph
1 In the Model Builder window, expand the Concentration (tds) node, then click Line Graph.
2 In the Settings window for Line Graph, locate the x-Axis Data section.
3 From the Parameter list, choose Expression.
4 In the Expression text field, type x.
5 From the Unit list, choose nm.
6 Click to expand the Legends section. Select the Show legends check box.
7 From the Legends list, choose Manual.
Legends
A+ Concentration
Line Graph 2
1 Right-click Results>Concentration (tds)>Line Graph and choose Duplicate.
2 In the Settings window for Line Graph, locate the y-Axis Data section.
3 In the Expression text field, type cX.
4 Locate the Legends section. In the table, enter the following settings:
Legends
X- Concentration
5 On the Concentration (tds) toolbar, click Plot.
1D Plot Group 3
1 On the Home toolbar, click Add Plot Group and choose 1D Plot Group.
2 In the Settings window for 1D Plot Group, type Surface Charge Density in the Label
text field.
3 Locate the Title section. From the Title type list, choose None.

Point Graph 1
1 Right-click Surface Charge Density and choose Point Graph.
4 In the Expression text field, type rho_surf.
7 Locate the Coloring and Style section. Find the Line style subsection. From the Line list,
choose None.
8 Find the Line markers subsection. From the Marker list, choose Circle.
9 From the Positioning list, choose In data points.
Legends
Surface charge density (simulation)
13 On the Surface Charge Density toolbar, click Plot.
Global 1
1 In the Model Builder window, under Results right-click Surface Charge Density and choose
Global.
2 In the Settings window for Global, locate the y-Axis Data section.
Expression Unit Description

Cd_GCS*phiM C/m^2 Surface charge density (theory)
6 Click to expand the Coloring and style section. Click to expand the Legends section.
Surface Charge Density

1 In the Model Builder window, under Results click Surface Charge Density.
2 In the Settings window for 1D Plot Group, locate the Plot Settings section.
3 Select the y-axis label check box.

4 In the associated text field, type Charge density (C/m2).
5 Click to expand the Legend section. From the Position list, choose Upper left.
6 On the Surface Charge Density toolbar, click Plot.

Desalination in an Electrodialysis Cell
Introduction
Electrodialysis is a separation process for electrolytes based on the use of electric fields and
ion selective membranes. Some common applications of the electrodialysis process are:
• Desalination of process streams, effluents, and drinking water

• pH regulation in order to remove acids from, for example, fruit juices and wines
• Metal electrowinning of precious metals
This tutorial demonstrates the basics of electrodialysis in a desalination cell.
2 | DESALINATION IN AN ELECTRODIALYSIS CELL

Model Definition
Figure 1shows the basic principle of the desalination stack. The stack has one repetitive cell
unit, shown in Figure 2.
Concentrate
Diluate
Electrode Electrode
Stream Stream
Cathode: Na + Na + Na + Na + Na + Na + Na + Na + Anode:
Negative Positive
Electrode Electrode
SO4 2- SO4 2- Cl - Cl - Cl - Cl - Cl - Cl - SO4 2-
H+
OH -
Electrode Electrode
Stream Stream
Diluate
Concentrate
Figure 1: Schematic picture of a desalination stack with 3 desalination units (in reality 10 -
20 unit cells are used)
Na + Na + Na +
Cl - Cl - Cl -
Figure 2: The repetitive unit cell with one desalination unit.

The model geometry for this example is based on the repetitive unit, excluding the inlet
and outlet flow regions. The model geometry is shown in Figure 3.
Outlets Dilutate channel
Cation selective membrane Anion selective membrane
Concentrate channels
Inlets
Figure 3: Model geometry.
The cell contains two ion selective membrane domains, the left is assumed to be permeable
to cations only, and the right to anions only. The middle domain is a free flowing
electrolyte domain, where salt is to be removed. This domain is named the dilutate
domain. The rightmost and leftmost domains are free flowing electrolyte domains, where
the ion concentration increases during cell operation. These domains are called the
concentrate domains. In the free electrolyte domains, the flow enters at the bottom inlets
and exits at the top outlets at an average flow rate is 5 mm·s-1. An analytical expression
(Poiseuille flow) for the fluid velocity is used in this model.
The cell is fed with a seawater electrolyte consisting of 0.5 M NaCl, and operated at a unit
cell voltage of 1.5 V.
CHOICE OF CURRENT DISTRIBUTION INTERFACE

In this model we may use of the Nernst-Planck equations for ion flux and charge transport
by which the following equation describes the molar flux of species i (which is either Cl or
Na in this model), Ni, due to diffusion, migration and convection:
N i = – D i ∇c i – z i u mob, i Fc i ∇φ l + c i u

The first term is the diffusion flux, Di is the diffusion coefficient (SI unit: m2/s). The
migration term consists of the species charge number zi, the species mobility umob,i
(SI unit: s·mol/kg) and the electrolyte potential ( φ l ). In the convection term, u denotes
the fluid velocity vector (SI unit: m/s).
The electrolyte current density is calculated using Faraday’s law by summing up the
contributions from the molar fluxes, multiplied by the species charges, with the
observation that the convective term vanishes due to the electroneutrality condition (see
the theory for the Tertiary Current Distribution, Nernst-Plank interface):
n
il = F  zi ( – Di ∇ci – zi um, i Fci ∇φl ) (1)

i=1
The conservation of current is then used to calculate the electrolyte potential.

n
∇ ⋅ il = F  zi Ri
i=1
where the Ri terms are the reaction sources due the porous electrode reactions.
This model uses Tertiary Current Distribution, Nernst-Planck interface when solving for
the electrolyte potential in the free electrolyte domains.
In the dilutate and concentrate domains, where there is free electrolyte present, the
gradients of Na+ and Cl- are not negligible. In the ion selective membranes, however, all
the counter ions are fixed in a matrix, implying that the concentration of the permeable
ion is constant. Therefore, due to electroneutrality, Equation 1 reduces to (here written
for Na+ in the cation selective membrane)
2
i l = – u m, + F c + ∇φ l = – σ l ∇φ l (2)
in the membrane, where σl is the electrolyte conductivity. Equation 2 is the equation used
in the Secondary Current Distribution interface.
Note that Equation 2 only concerns the governing equation for the electrolyte potential
in the membrane. Transport of additional trace species in the membrane, with minor
impact on the total charge transport, can be added to the model using the Transport of
Diluted Species interface.

MEMBRANE—FREE ELECTROLYTE BOUNDARY CONDITIONS
The boundary conditions at the boundaries between the Secondary Current Distribution
interface for the membrane and the Tertiary Current Distribution, Nernst-Planck interface
are set up in the following way:
The normal electrolyte current density is equal to the current density in the membrane:
n ⋅ i l, e = n ⋅ i l, m (3)
The ion flux for the permeable ion is proportional to the current, according to Faraday’s
law
i l, m
n ⋅ N i, e = n ⋅ ---------- (4)
zi F
For the non-permeable ion, the flux is zero.
Furthermore, we have the following relation between the potentials and the
concentrations:
c i, m
φ l, m = φ l, e + -------- ln  ----------
RT
(5)
F c i, e
where ci,m is the permeable ion concentration in the membrane, and ci,e the permeable
ion concentration in the free electrolyte. The potential shift caused by Equation 5 is called
Donnan potential, or dialysis potential.
Equation 3, Equation 4, and Equation 5 above represent a mix a Dirichlet and Neumann
conditions for three different dependent variables (two potentials and one concentration).
The Ion Exchange Membrane Boundary feature in the Tertiary Current Distribution,
Nernst-Planck interface is used to define these conditions.
COUPLING BETWEEN THE OUTER CONCENTRATE BOUNDARIES

Use a linear extrusion operator to set the concentration on the rightmost boundary to
equal that of the leftmost boundary.

Figure 4 shows the ion concentration in the cell. The concentration increases in the
concentrate domains, and decreases in the dilutate domain. A boundary layer with high
concentration gradients forms close to the membrane surfaces. In a real desalination cell
it is common to add spacers that, apart from adding mechanical stability to the cell, also

induce convective mass transport in the direction perpendicular to the main flow, and
hence may reduce the thickness of the boundary layer.
Figure 4: Ion concentration.
Figure 5 shows the electrolyte potential along a horizontal line placed at half the cell
height. The main part of the potential losses occurs in the membranes. The Donnan
potential discontinuity can be seen at the boundaries between the free electrolyte and
membrane domains.

Figure 5: Electrolyte potential at half the cell height.
Figure 6 shows the concentration at half the cell height for three different cell potentials,
0.5, 0.8, and 1.1 V. The concentration gradients increase with higher potentials.

Figure 6: Ion concentration at half the cell height for different unit cell voltages.
Figure 7 and Figure 8 show a comparison between the migrative and diffusive fluxes in the
free electrolyte for Na+ and Cl-, respectively. The diffusive fluxes get prominent close to
the membrane boundaries due to the high concentration gradients. The migrative fluxes
govern in the middle of the channels and have different signs for Na+ and Cl- due to the
different signs of the ion charges.

Figure 7: Comparison of fluxes, species Na+.
Figure 8: Comparison of fluxes, species Cl-.

Finally, Figure 9 shows the current density along the left free electrolyte – membrane
boundary of the anion selective membrane for three different cell voltage levels. Depletion
of chloride gets more prominent towards the top of the cell, resulting in a higher Donnan
potential shift and a higher current density. Increasing the cell voltage further increases the
cell current somewhat more, but the cell eventually reaches a limiting current density.
Figure 9: Normal current density along the membrane – free electrolyte boundary for the
anion selective membrane for three different cell voltages (0.5 V, 1.0 V, and 1.5 V).

Electrochemical_Engineering/electrodialysis
NEW
MODEL WIZARD

2 In the Select Physics tree, select Electrochemistry>Tertiary Current Distribution, Nernst-
Planck>Tertiary, Electroneutrality (tcd).
3 Click Add.
cNa
cCl

6 Click Add.
7 In the Electrolyte potential text field, type phil_m.
8 Click Study.
9 In the Select Study tree, select Preset Studies for Selected Physics Interfaces>Stationary.
10 Click Done.
GLOBAL DEFINITIONS
Parameters
Load the model parameters from a text file.

electrodialysis_parameters.txt.
GEOMETRY 1
Draw the geometry as a set of rectangles.
Rectangle 1 (r1)
3 In the Width text field, type 2*(W_ch+W_m).
4 In the Height text field, type L.
5 Locate the Position section. In the x text field, type -(W_ch+W_m).
6 Right-click Rectangle 1 (r1) and choose Build Selected.

Rectangle 2 (r2)
3 In the Width text field, type (W_ch+2*W_m).
5 Locate the Position section. In the x text field, type -(W_ch+2*W_m)/2.
Rectangle 3 (r3)
3 In the Width text field, type W_ch.
5 Locate the Position section. In the x text field, type -W_ch/2.
The finished geometry should look like Figure 3 in the Model Definition section.
DEFINITIONS
Make some selections on the geometry to use later when you set up the physics.
Explicit 1
1 On the Definitions toolbar, click Explicit.
2 Select Domains 2 and 4 only.
3 Right-click Explicit 1 and choose Rename.
4 In the Rename Explicit dialog box, type Membranes in the New label text field.
5 Click OK.
Explicit 2
2 Select Domains 1, 3, and 5 only.
4 In the Rename Explicit dialog box, type Channels in the New label text field.
5 Click OK.

Explicit 3
2 In the Settings window for Explicit, locate the Input Entities section.
4 Select Boundaries 2, 8, and 14 only.
6 In the Rename Explicit dialog box, type Inlets in the New label text field.
7 Click OK.
Explicit 4
2 In the Settings window for Explicit, locate the Input Entities section.
4 Select Boundaries 3, 9, and 15 only.
6 In the Rename Explicit dialog box, type Outlets in the New label text field.
7 Click OK.
Linear Extrusion 1 (linext1)

Create a linear extrusion from the leftmost boundary to the rightmost boundary. It will be
used later to couple the concentrations on each side of the cell together.
1 On the Definitions toolbar, click Component Couplings and choose Linear Extrusion.
2 In the Settings window for Linear Extrusion, locate the Source Selection section.
5 Locate the Source Vertices section. Select the Active toggle button.
6 Select Point 1 only.
7 Select the Active toggle button.
9 Locate the Destination Vertices section. Select the Active toggle button.

Variables 1
Now add some variables to the model.
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.
5 Locate the Variables section. In the table, enter the following settings:
Name Expression Unit Description

vel 3*v_avg*(1-((x)/(W_ch/ m/s Channel velocity (middle
2))^2) channel)
Variables 2

vel 3*v_avg*(1-((x+W_ch+ m/s Channel velocity (left
W_m)/(W_ch/2))^2) channel)
Variables 3

vel 3*v_avg*(1-((x-W_ch- m/s Channel velocity (right
W_m)/(W_ch/2))^2) channel)
TE R T I A R Y C U R R E N T D I S T R I B U T I O N , N E R N S T - P L A N C K ( T C D )
Now start setting up the physics, start with the free electrolyte channels.

1 In the Model Builder window, under Component 1 (comp1) click
Tertiary Current Distribution, Nernst-Planck (tcd).
2 In the Settings window for Tertiary Current Distribution, Nernst-Planck, locate the
Domain Selection section.
3 From the Selection list, choose Channels.
Electrolyte 1
1 In the Model Builder window, under Component 1 (comp1)>Tertiary Current Distribution,
Nernst-Planck (tcd) click Electrolyte 1.
2 In the Settings window for Electrolyte, locate the Model Input section.
4 Locate the Convection section. Specify the u vector as
0 x
vel y
5 Locate the Diffusion section. In the DcNa text field, type DNa.
6 In the DcCl text field, type DCl.
7 Locate the Migration in Electric Field section. In the zcNa text field, type 1.
8 In the zcCl text field, type -1.
3 In the Settings window for Electrolyte Potential, locate the Electrolyte Potential section.
4 In the φl, bnd text field, type Vtot.
Concentration 1
4 Select the Species cCl check box.

5 In the c0,cCl text field, type comp1.linext1(cCl).
This condition sets the concentration on the rightmost boundary to be equal its
corresponding value on the leftmost boundary.
Inflow 1
1 On the Physics toolbar, click Boundaries and choose Inflow.
2 In the Settings window for Inflow, locate the Boundary Selection section.
3 From the Selection list, choose Inlets.
4 Locate the Concentration section. In the c0,cCl text field, type cCl_0.
5 Locate the Boundary Condition Type section. From the list, choose Flux (Danckwerts).
Outflow 1
1 On the Physics toolbar, click Boundaries and choose Outflow.
2 In the Settings window for Outflow, locate the Boundary Selection section.
3 From the Selection list, choose Outlets.
Ion Exchange Membrane Boundary 1

The boundary condition at the cation selective membrane is set as follows. The electrolyte
potential in the membrane is coupled to the electrolyte potential and Na+ concentration
in the porous electrode by the use of Donnan potential expression on the boundaries
between the membrane and the porous electrode.
1 On the Physics toolbar, click Boundaries and choose Ion Exchange Membrane Boundary.
2 Select Boundaries 4 and 7 only.
3 In the Settings window for Ion Exchange Membrane Boundary, locate the Model Input
section.
5 Locate the Ion Exchange Membrane Boundary section. From the φm list, choose
Electrolyte potential (cd).
6 In the cm text field, type cNam.
Ion Exchange Membrane Boundary 2

Similarly, the boundary condition at the anion selective membrane is set as follows. The
electrolyte potential in the membrane is coupled to the electrolyte potential and Cl−
concentration in the porous electrode by the use of Donnan potential expression on the
boundaries between the membrane and the porous electrode.
1 On the Physics toolbar, click Boundaries and choose Ion Exchange Membrane Boundary.

3 In the Settings window for Ion Exchange Membrane Boundary, locate the Model Input
section.
5 Locate the Ion Exchange Membrane Boundary section. From the cl list, choose cCl.
6 From the φm list, choose Electrolyte potential (cd).
7 In the cm text field, type cClm.
Initial Values 1
Nernst-Planck (tcd) click Initial Values 1.
3 In the cCl text field, type cCl_0.

Now set up the physics for the membranes.
On the Physics toolbar, click Tertiary Current Distribution, Nernst-Planck (tcd) and choose
Secondary Current Distribution (cd).

2 In the Settings window for Secondary Current Distribution, locate the Domain Selection
section.
3 From the Selection list, choose Membranes.
Electrolyte 1
Secondary Current Distribution (cd) click Electrolyte 1.
2 In the Settings window for Electrolyte, locate the Electrolyte section.
3 From the σl list, choose User defined. In the associated text field, type sigma_m.
Change to second order elements to match the second order elements of the tertiary
current distribution interface.
4 In the Model Builder window’s toolbar, click the Show button and select Discretization in
the menu.
5 In the Model Builder window, click Secondary Current Distribution (cd).

6 In the Settings window for Secondary Current Distribution, click to expand the
Discretization section.
7 From the Electrolyte potential list, choose Quadratic.
MESH 1
The physics settings are now complete. A mapped mesh is suitable for this geometry. Use
distributions to obtain thinner elements in the free electrolyte close to the membrane
surfaces.
Distribution 1
Mapped.
2 Right-click Mapped 1 and choose Distribution.
4 In the Settings window for Distribution, locate the Distribution section.
5 In the Number of elements text field, type 100.
Distribution 2
4 From the Distribution properties list, choose Predefined distribution type.
6 In the Element ratio text field, type 10.
7 Select the Symmetric distribution check box.
Distribution 3
7 Select the Reverse direction check box.

Distribution 4
Distribution 5
Distribution 6
Distribution 7

STUDY 1
Step 1: Stationary
The problem is now ready for solving. Use an auxiliary sweep to solve for a range of
potentials.
3 Click Add.

Vtot (Total potential drop over range(0.5,0.3,1.1)
unit cell)
Solution 1 (sol1)
1 On the Study toolbar, click Show Default Solver.
2 In the Model Builder window, expand the Solution 1 (sol1) node.
3 In the Model Builder window, under Study 1>Solver Configurations>Solution 1 (sol1) click
Stationary Solver 1.
4 In the Settings window for Stationary Solver, locate the General section.
5 In the Relative tolerance text field, type 1e-5.
RESULTS
Concentration (tcd)
Reproduce the figures from the Results and Discussion section in the following way.
1 On the Concentration (tcd) toolbar, click Plot.
Cut Line 2D 1
1 On the Results toolbar, click Cut Line 2D.
2 In the Settings window for Cut Line 2D, locate the Line Data section.
3 In row Point 1, set X to -W_ch-W_m and y to L/2.
4 In row Point 2, set X to W_ch+W_m and y to L/2.
5 Click Plot.

1D Plot Group 6
1 On the Results toolbar, click 1D Plot Group.
3 From the Data set list, choose Cut Line 2D 1.
4 From the Parameter selection (Vtot) list, choose Last.
Line Graph 2
1 Right-click 1D Plot Group 6 and choose Line Graph.
4 In the Expression text field, type phil_m.
1D Plot Group 6
1 In the Model Builder window, under Results click 1D Plot Group 6.
2 In the Settings window for 1D Plot Group, click to expand the Title section.
3 From the Title type list, choose None.
4 On the 1D Plot Group 6 toolbar, click Plot.
1D Plot Group 7
Line Graph 1
3 In the Expression text field, type cNa.
1D Plot Group 8
4 From the Parameter selection (Vtot) list, choose Last.

Line Graph 1
3 In the Expression text field, type tcd.tfluxx_cNa.
4 Locate the Legends section. Select the Show legends check box.
Legends
Total Flux
Line Graph 2
1 Right-click Results>1D Plot Group 8>Line Graph 1 and choose Duplicate.
3 In the Expression text field, type tcd.mflux_cNax.
Legends
Migrative Flux
Line Graph 3
1 Right-click Results>1D Plot Group 8>Line Graph 2 and choose Duplicate.
3 In the Expression text field, type tcd.dflux_cNax.
Legends
Diffusive Flux
1D Plot Group 8
2 In the Settings window for 1D Plot Group, locate the Plot Settings section.

3 Select the x-axis label check box.
4 In the associated text field, type Position.
6 In the associated text field, type Flux.
7 Locate the Title section. From the Title type list, choose Manual.
8 In the Title text area, type Na+ flux, x component (mol/(m2*s)).
Line Graph 1
1 Right-click Results>1D Plot Group 8 and choose Duplicate.
2 In the Model Builder window, expand the 1D Plot Group 9 node, then click Line Graph 1.
4 In the Expression text field, type tcd.tfluxx_cCl.
Line Graph 2
1 In the Model Builder window, under Results>1D Plot Group 9 click Line Graph 2.
3 In the Expression text field, type tcd.mflux_cClx.
Line Graph 3
1 In the Model Builder window, under Results>1D Plot Group 9 click Line Graph 3.
3 In the Expression text field, type tcd.dflux_cClx.
1D Plot Group 9
2 In the Settings window for 1D Plot Group, locate the Title section.
3 In the Title text area, type Cl- flux, x component (mol/(m2*s)).
Line Graph 1
2 In the Model Builder window, right-click 1D Plot Group 10 and choose Line Graph.

3 In the Settings window for Line Graph, locate the Selection section.
6 Click Replace Expression in the upper-right corner of the y-axis data section. From the
menu, choose Component 1>Secondary Current Distribution>cd.nIl -
Normal electrolyte current density.
8 In the Expression text field, type y.
9 Locate the Legends section. Select the Show legends check box.
1D Plot Group 10
1 In the Model Builder window, under Results right-click 1D Plot Group 10 and choose
Rename.
2 In the Rename 1D Plot Group dialog box, type Electrolyte current density in the
New label text field.
3 Click OK.
1D Plot Group 9
Rename.
2 In the Rename 1D Plot Group dialog box, type Fluxes, Cl in the New label text field.
3 Click OK.
1D Plot Group 8
Rename.
2 In the Rename 1D Plot Group dialog box, type Fluxes, Na in the New label text field.
3 Click OK.
1D Plot Group 7
Rename.
2 In the Rename 1D Plot Group dialog box, type Concentration in the New label text
field.
3 Click OK.

1D Plot Group 6
Rename.
2 In the Rename 1D Plot Group dialog box, type Potential in the New label text field.
3 Click OK.

Glucose Sensor
Introduction
Glucose sensing is one of the most widespread and commercially successful uses of
electroanalysis. In an electrochemical glucose sensor, the concentration of glucose in a
sample is measured using amperometry; that is, the measurement of an electric current.
An applied voltage causes the oxidation of glucose, and the current due to this oxidation
is measured at the electrode. In a well designed glucose sensor, there is a linear relationship
between the glucose concentration and the current, enabling a calibrated measurement.
Typically, the oxidation of glucose does not occur directly at the working electrode where
current is measured. Instead, the reaction is accomplished by a chemical oxidant and
accelerated by a biological enzyme such as glucose oxidase (GOx), which makes the sensor
specific to glucose and independent of the concentration of other oxidizable species that
may be present in the analyte solution.
The reduced form of the oxidant, after its reaction with glucose, can be re-oxidized
directly at the electrode. In nature, the oxidant is oxygen, but this suffers from slow
kinetics and the rate of oxidation is perturbed by the oxygen concentration dissolved from
atmosphere into the analyte solution.
Instead an inorganic oxidant with fast electrode kinetics, such as the hexacyanoferrate (III)
anion (commonly, “ferricyanide”), is suitable for use in a glucose sensor, since the
measured current is made independent of oxygen concentration and is not limited by slow
electrode kinetics (Ref. 1).
This example demonstrates a steady-state analysis of the current drawn in a unit cell of
solution above an interdigitated electrode, where the counter electrode reacts ferricyanide
to ferrocyanide. The linearity of the response of the sensor is demonstrated for a typical
range of glucose concentrations.
Model Definition
The model contains a single 2D domain representing a 100 μm-wide unit cell of solution
above an interdigitated electrode (Figure 1). The real geometry is a periodic repetition of
this unit cell in the x-direction. The cell and electrode are assumed to extend sufficiently
far out-of-plane of the model that the 2D approximation is suitable.
At the top of the unit cell is a bulk boundary where the concentrations are assumed to
equal those in the bulk solution of the analyte. At the bottom of the unit cell, the y = 0
axis is divided by four points into separate electrode and insulator boundaries. The anode
(working electrode) is at the center of the cell in the range 37.5 μm < x < 62.5 μm. The
2 | GLUCOSE SENSOR
unit cell contains half of each of the two neighboring cathodes (counter electrodes) in the
ranges x < 12.5 μm and x > 87.5 μm. Between the anode and cathode surfaces, a solid
insulating material is present.
Figure 1: Model Geometry.
A large quantity of supporting electrolyte is present. This is inert salt added in
electroanalytical experiments to increase the conductivity of the electrolyte without
otherwise interfering with the reaction chemistry. Under these conditions, the resistance
of the solution is sufficiently low that the electric field is negligible, and we can assume a
constant electrolyte potential φl = 0.
The Electroanalysis interface implements chemical species transport equations to describe

the diffusion of the chemical species. The domain equation is the diffusion equation (also
known as Fick’s 2nd law). At steady-state, this reduces to:
∇ ⋅ ( D i ∇c i ) = 0
for each species i. In this model three species are modeled: the active redox couple—
ferricyanide and ferrocyanide anions—as well as the concentration of the glucose analyte
3 | GLUCOSE SENSOR
species. We ignore the products of the glucose oxidation since they do not affect the
behavior of the sensor.
The enzyme-mediated reaction of the glucose with the ferricyanide anion occurs in the
solution phase above the electrode:
glucose + ferri ↔ products + ferro
The rate of this reaction (mol/m3) is given by a Michaelis–Menten rate law as (Ref. 2):
c glucose V max
R = -----------------------------------------
( 1 + K m c glucose )
Here, the parameter Vmax is the maximum rate of the enzyme-catalyzed reaction,
depending on the quantity of enzyme available, and the parameter Km is a characteristic
Michaelis-Menten coefficient. At large glucose concentration, the rate becomes
independent of the glucose concentration and solely depends on the enzyme kinetics.
At the bulk boundary (y = 1 mm), we assume a uniform concentration of each chemical
species equal to its bulk concentration. The glucose concentration here is equivalent to
that in the analyte mixture being measured; the ferricyanide:ferrocyanide ratio here is 50
000:1, with the ferricyanide anion present in bulk in a concentration of 50 mM. Because
the analytical process is oxidizing with respect to the glucose analyte, more oxidant must
be supplied.
At the insulating (inert) surfaces, the normal fluxes of all species are equal to zero, since
this surface is impermeable and no species reacts there.
At the electrode boundaries, current is drawn from the interconversion of ferrocyanide and
ferricyanide. By convention, electrochemical reactions are written in the reductive
direction:
–
ferri + e ↔ ferro
The stoichiometric coefficient is –1 for ferricyanide, the “reactant” in the reductive

direction, and +1 for ferrocyanide, the “product” in the reductive direction. This
formulation is consistent at the anode also, although here the reaction proceeds favorably
in the opposite, oxidative direction. The number of electrons transferred, n, equals one.
The current density for this reaction is given by the electroanalytical Butler–Volmer
4 | GLUCOSE SENSOR
i loc = nFk 0  c ferro exp  ---------------------------- – c ferri exp  ----------------- 
  RT   RT  
coefficient, and η is the overpotential at the working electrode.
ν i i loc
– n ⋅ N i = -------------
nF
The total current recorded at the electrode can be extracted by integrating the local
current density across the electrode surface. It is not sufficient to simply multiply by the
area of the electrode, because the current density may be non-uniform. An Integration
Component Coupling is used to define an electrode current variable according to:
I el =  iloc dA
S
where the integration is performed over the area of the working electrode.
The working electrode (anode) is held at +0.4 V vs. the ferro/ferricyanide redox couple.
The counter electrode is constrained to deliver an opposite current to the anode.
S TAT I O N A RY S T U DY
This model calculates the steady-state current delivered under a constant applied potential.
Therefore a Stationary study is chosen. A Parametric Sweep is used to compare the
currents and concentration profiles for different external glucose concentrations in the
analyte solution.

Figure 2 shows a typical concentration profile for the ferrocyanide ion in the unit cell.
Ferrocyanide is generated in the solution between the electrodes and bulk by the enzyme-
catalyzed oxidation of glucose. It reacts at the anode in the center of the unit cell to
provide the working electrode current used to measure the concentration of glucose.
Ferrocyanide is regenerated at the cathode counter electrodes at the left and right of the
cell.
5 | GLUCOSE SENSOR
The diffusion of ferrocyanide from the counter to the working electrode is an example of
a “redox cycling” process where a single redox reaction is driven in opposite directions at
two electrodes with a small geometric separation. This cycling effect amplifies the current
and so ensures a linear response to a wide range of glucose concentrations, as illustrated in
Figure 3.
Figure 2: Ferrocyanide concentration for an external glucose concentration of 1 mol/m3.
6 | GLUCOSE SENSOR
Figure 3: Current density versus glucose concentration.
References
1. J. Wang, “Electrochemical Glucose Biosensors,” Chem. Rev., vol. 108, no. 2, pp. 814–
825, 2008.
2. P. Atkins and J. de Paula, Physical Chemistry, 9th ed., W. H. Freeman and Company,
New York, 2010.
Application Library path: Electrochemistry_Module/Electroanalysis/

glucose_sensor
NEW
7 | GLUCOSE SENSOR
MODEL WIZARD
Build the model in 2D with the Electroanalysis interface. Solve for three concentrations in
a Stationary study.

3 Click Add.
c_glucose
c_ferro
c_ferri
6 Click Study.
8 Click Done.
GEOMETRY 1
Set the length unit to micrometers and create the geometry using a rectangle and an array
of points.

3 From the Length unit list, choose µm.
Rectangle 1 (r1)
3 In the Width text field, type 100.
Point 1 (pt1)
1 On the Geometry toolbar, click Primitives and choose Point.
2 In the Settings window for Point, locate the Point section.
3 In the x text field, type 12.5.
8 | GLUCOSE SENSOR
Array 1 (arr1)
1 On the Geometry toolbar, click Transforms and choose Array.
2 Select the object pt1 only.
3 In the Settings window for Array, locate the Size section.
4 In the x size text field, type 4.
5 Locate the Displacement section. In the x text field, type 25.
6 Right-click Array 1 (arr1) and choose Build Selected.
Your finished geometry should now look like this:
GLOBAL DEFINITIONS
Import the model parameters from a text file.
Parameters
glucose_sensor_parameters.txt.
9 | GLUCOSE SENSOR
DEFINITIONS
Add an average operator that will be used to calculate the average of the current density
over one of the electrode surfaces.
Average 1 (aveop1)
1 On the Definitions toolbar, click Component Couplings and choose Average.
2 In the Settings window for Average, locate the Source Selection section.
Variables 1

R_MM V_max*c_glucose/ mol/(m³·s) Reaction rate of glucose
(Km+c_glucose)
i_avg aveop1(elan.itot) Average current density
The i_avg variable in marked in orange. This is because the itot variable has not yet been
defined. It will be defined and added automatically to the model later on when you add
the Electrode Surface feature.
Now start defining the physics.
Electrode Surface 1
4 In the φs, ext text field, type 0.4.
2 In the Settings window for Electrode Reaction, locate the Stoichiometric Coefficients
section.
3 In the νcferro text field, type 1.
10 | GLUCOSE SENSOR
4 In the νcferri text field, type -1.
Electrode Surface 2
4 From the Boundary condition list, choose Counter electrode.
5 In the φs, ext, init text field, type 0.1.
2 In the Settings window for Electrode Reaction, locate the Stoichiometric Coefficients
section.
3 In the νcferro text field, type 1.
4 In the νcferri text field, type -1.
Concentration 1
4 Select the Species c_glucose check box.
5 In the c0,cglucose text field, type c_glucose_ext.
6 Select the Species c_ferro check box.
7 In the c0,cferro text field, type c_ferro_ext.
8 Select the Species c_ferri check box.
9 In the c0,cferri text field, type c_ferri_ext.
Reactions 1
1 On the Physics toolbar, click Domains and choose Reactions.
2 Click in the Graphics window and then press Ctrl+A to select all domains.
3 In the Settings window for Reactions, locate the Reaction Rates section.
4 In the Rcglucose text field, type -R_MM.
5 In the Rcferro text field, type R_MM.
6 In the Rcferri text field, type -R_MM.
11 | GLUCOSE SENSOR
Initial Values 1
Initial Values 1.
3 In the cglucose text field, type c_glucose_ext.
4 In the cferro text field, type c_ferro_ext.
5 In the cferri text field, type c_ferri_ext.
MESH 1
The physics settings are now complete. Now customize the mesh and solve the problem.
Edit Physics-Induced Sequence.
Size
1 In the Model Builder window, under Component 1 (comp1)>Mesh 1 click Size.
3 From the Predefined list, choose Extra fine.
Size 1
1 In the Model Builder window, under Component 1 (comp1)>Mesh 1 right-click
Free Triangular 1 and choose Size.
4 Select Boundaries 2 and 4–7 only.
5 Locate the Element Size section. From the Predefined list, choose Extremely fine.
6 Click the Custom button.
8 In the associated text field, type 1.
12 | GLUCOSE SENSOR
Your finished mesh should now look like this:
STUDY 1
Use an auxiliary sweep to solve for a range of different external concentration values for
c_glucose_ext.
Step 1: Stationary
1 In the Model Builder window, under Study 1 click Step 1: Stationary.
4 Click Add.
5 Click to select row number 1 in the table.

c_glucose_ext range(50,50,1000) umol/L
13 | GLUCOSE SENSOR
RESULTS
Concentration (elan)
Modify the default concentration plot to show the ferro concentration.
Surface 1
1 In the Model Builder window, expand the Concentration (elan) node, then click Surface 1.
2 In the Settings window for Surface, locate the Expression section.
3 In the Expression text field, type c_ferro.
4 On the Concentration (elan) toolbar, click Plot.
1D Plot Group 2
Create a plot of the average current density for different c_ferro_ext values as follows:
2 In the Settings window for 1D Plot Group, type Average Current Density in the Label
text field.
Global 1
1 Right-click Average Current Density and choose Global.

i_avg A/m^2 Average current density
4 Click to expand the Legends section. Clear the Show legends check box.
5 On the Average Current Density toolbar, click Plot.
14 | GLUCOSE SENSOR
Electrochemical Impedance Spectroscopy
Introduction
Electrochemical impedance spectroscopy is a common technique in electroanalysis. It is
used to study the harmonic response of an electrochemical system. A small, sinusoidal
variation is applied to the potential at the working electrode, and the resulting current is
analyzed in the frequency domain.
The real and imaginary components of the impedance give information about the kinetic
and mass transport properties of the cell, as well as its capacitive properties. By measuring
impedance at a range of frequencies, the relative influence of the various constituent
physics of the system can be interpreted as a function of time scale.
As in electrical analysis, the real component of impedance corresponds to a resistance in-

phase with the applied voltage. The imaginary component corresponds to a reactance 90°
out-of-phase with the applied voltage; the reactance is caused by capacitive charging in the
cell.
Capacitive charging occurs at the double layer adjacent to the working electrode surface.
Here, the net charge on the electrode causes accumulation or depletion of charged ions in
the neighboring solution; as the potential on the electrode changes, so does its charge, and
so the double layer charges and discharges with a characteristic capacitance.
In this example, the AC Impedance, Initial Values study type is used to perform a
linearized perturbation study in the frequency domain around the provided initial values
to resolve the magnitude and phase of the current response to the sinusoidal voltage. A
Parametric Sweep is used to compare the response of the system with different electrode
kinetics for the redox couple.
Model Definition
This model contains a single 1D domain. The length of the domain, L (m), is based on
the diffusion coefficient, D (m2/s) and lowest frequency, fmin(1/s), in order to be
sufficiently large compared to the timescale of diffusion (the diffusion layer).
D -
L = 10 ---------------- (1)
2πf min
2 | ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY

assume φl = 0.
The Electroanalysis interface implements chemical transport equations for the reactant and
product species of the redox couple subject to this assumption. The domain equation is
the diffusion equation (also known as Fick’s 2nd law) to describe the chemical transport
of the electroactive species A and B:
∂c i
------- = ∇ ⋅ ( D i ∇c i )
∂t
Both the oxidized and reduced species are equally concentrated at ci = 1 μM in bulk
(x = L).
At the working electrode surface (x = 0), the reactant species A oxidizes (loses one
electron) to form the product B. By convention, electrochemical reactions are written in
the reductive direction:
–
B+e ↔A
1 for A, the “product” in the reductive direction. The number of electrons transferred, n,
equals one.
i loc = nFk 0  c A exp  ---------------------------- – c B exp  -----------------  (2)
  RT   RT  
coefficient, and η is the overpotential at the working electrode. This overpotential is the
difference between the applied potential and the equilibrium potential (formal reduction
potential) of the redox couple of species A and B, Eeq:
η = φ s, ext – E eq

ν i i loc
– n ⋅ N i = ------------- (3)
nF
An additional capacitance is applied at the working electrode. It is set equal to 20 μF/cm2

which is a typical value for a water-metal interface. The real value of this capacitance can
be established by impedance spectroscopy of the blank solution containing only the
supporting electrolyte, or by an alternative voltammetric method.
A C I M P E D A N C E S T U DY
The AC Impedance study is used to model a harmonic perturbation applied to a fixed
center electrode potential, which in this case is fixed to the equilibrium potential of the
redox couple:
jωt
φ s, ext = E eq + Δφe
where it is implied that only the real part of the complex term contributes.
The magnitude of this perturbation, Δφ, is small with respect to RT/F, so that the Butler-
Volmer equation (Equation 2) can be linearized. Therefore, the system responds linearly
to the perturbation, and the flux (Equation 3), the concentration profiles, and the current
density are all also subject to a sinusoidal perturbation at the same frequency.
The AC Impedance Study makes the approximation that the dependent variables ci can be
expressed as the sum of a stationary solution ci,0 due to the center voltage of the applied
potential, and a sinusoidal perturbation ci,1 to the concentration resulting from the
perturbation on the applied potential:
jωt
c i ( x, t ) = c i, 0 ( x ) + c i, 1 ( x )e
If ci,1 is complex, it implies that the response of the concentration profile is out-of-phase
with the applied waveform.
The AC Impedance Initial Values study contains a Frequency Domain study step that
solves for the perturbation around the provided initial values, for a range of applied
frequencies from 1 Hz to 1 kHz. In each case the domain equation is the frequency
domain form of Fick’s 2nd Law:
jωc i, 1 = ∇ ⋅ ( D i ∇c i, 1 )
solved subject to ci,1 = 0 in bulk and:

φ s, ext = Δφ
at the surface.
A Parametric Sweep is used to investigate different values of the heterogeneous rate

constant of the electrode reaction, k0, from a value that is kinetically fast on the timescale
of the study (0.1 cm/s) to one that it is slow on the same timescale (0.001 cm/s).

A Nyquist plot (Figure 1) is the most common means of plotting the results of an
impedance experiment. It is an Argand diagram of the complex value of the impedance as
a function of frequency; the real component of impedance (resistance) is plotted on the x-
axis, and the imaginary component (reactance) is plotted on the y-axis.
For a fast electrochemical reaction with respect to the frequency of the electrochemical
impedance study, the impedance always results from the limitation to the current due to
the finite diffusivity of the redox species in the solution. It is known from theory that the
real and imaginary impedances are linearly correlated in this “transport-controlled”
regime (Figure 1).
For a slow electrochemical reaction with respect to the frequency, the mass transport is
unimportant as the rate of electron transfer is limited by the rate of reaction at the surface:
this is the “kinetically controlled” regime. This regime is characterized by a semi-circular
Nyquist plot.
It is common to observe both regimes in a single plot, since the relevant timescale of the
experiment changes with the frequency of the harmonic perturbation. At low frequency,
mass transport dominates, but at high frequency (towards the bottom-left of the plot),

there is a transition to kinetic control. This transition is most marked for the slowest
electrochemical reaction studied, where k0 = 0.001 cm/s.
Figure 1: Nyquist plot showing the relation of real to imaginary impedance for a range of
frequencies and a range of electrode kinetic heterogeneous rate constants.
In a Bode plot, either the magnitude (Figure 2) or the phase (Figure 3) of the complex
impedance is plotted against frequency on the x-axis.

Figure 2: Bode plot showing the magnitude of impedance as a function of frequency for a
range of electrode kinetic heterogeneous rate constants.
Figure 3: Bode plot showing the phase of the impedance as a function of frequency for a range
of electrode kinetic heterogeneous rate constants.

Depending on whether a reaction proceeds under kinetic or transport control at a certain
frequency, the Bode plots have different characteristic appearances. Ref. 1. gives a
comprehensive discussion and references to further literature concerning the analysis of
electrochemical impedance spectra.
Reference
Applications, 2nd ed., Wiley, New York, 2001.

impedance_spectroscopy
NEW
MODEL WIZARD
3 Click Add.
cRed
cOx
5 Click Study.
Use an AC Impedance, Initial Values study type in this model. This study will set up a
suitable solver sequence for your problem.
6 In the Select Study tree, select Preset Studies>AC Impedance, Initial Values.
7 Click Done.

GLOBAL DEFINITIONS
Parameters

impedance_spectroscopy_parameters.txt.
GEOMETRY 1
Build the model geometry as a single interval of length L_el. (The parameter was included
in the list of parameters that was loaded from the text file.)
Interval 1 (i1)
3 In the Right endpoint text field, type L_el.
4 Click Build All Objects.
Now set up the physics. Start with the diffusion coefficients for cOx and cRed.

3 In the DcRed text field, type D.
4 In the DcOx text field, type D.
Initial Values 1
Initial Values 1.
3 In the cRed text field, type c_bulk.

4 In the cOx text field, type c_bulk.
Concentration 1
4 Select the Species cRed check box.
5 In the c0,cRed text field, type c_bulk.
6 Select the Species cOx check box.
7 In the c0,cOx text field, type c_bulk.
Add an Electrode Surface boundary node and specify the voltage perturbation, the
electrode reaction, and the double layer capacitance.
Electrode Surface 1
3 In the Settings window for Electrode Surface, click to expand the Harmonic perturbation
section.
4 Locate the Harmonic Perturbation section. In the Δφs, ext text field, type V_app.
2 In the Settings window for Electrode Reaction, locate the Electrode Kinetics section.
3 In the k0 text field, type k0.
4 Locate the Stoichiometric Coefficients section. In the νcRed text field, type 1.
5 In the νcOx text field, type -1.
Double Layer Capacitance 1

1 In the Model Builder window, under Component 1 (comp1)>Electroanalysis (elan) right-
click Electrode Surface 1 and choose Double Layer Capacitance.
2 In the Settings window for Double Layer Capacitance, locate the Double Layer Capacitance
section.
3 In the Cdl text field, type Cdl.
MESH 1

3 From the Element size list, choose Extremely fine.
Modify the default mesh by specifying the maximum element size on the electrode
surface as a multiple of the shortest diffusion length (highest frequency).
4 Right-click Component 1 (comp1)>Mesh 1 and choose Edit Physics-Induced Sequence.
Size 1
1 In the Model Builder window, under Component 1 (comp1)>Mesh 1 click Size 1.
7 In the associated text field, type xdiff_min/25.
STUDY 1
The model is now ready for solving. Add a parametric sweep to study the effect when
varying the k0 parameter value for a range of frequencies.
Parametric Sweep
3 Click Add.

k0 (Heterogeneous rate constant) 10^range(-1,-1,-3) cm/s
Step 1: Frequency Domain Perturbation

1 In the Model Builder window, under Study 1 click Step 1: Frequency Domain Perturbation.
2 In the Settings window for Frequency Domain Perturbation, locate the Study Settings
section.
3 In the Frequencies text field, type 10^range(log_freq_min,0.05,log_freq_max).

RESULTS
Impedance vs Ground, Nyquist (elan)

A Nyquist plot, and plots of the real and imaginary parts of the impedance, are created by
default.
1 In the Model Builder window, under Results click Impedance vs Ground, Nyquist (elan).
2 In the Settings window for 1D Plot Group, click to expand the Legend section.
3 From the Position list, choose Lower right.
4 On the Impedance vs Ground, Nyquist (elan) toolbar, click Plot.
Impedance vs Ground, Real Part (elan)

Create plots of the magnitude (absolute value) and the phase angle as follows:
Impedance vs Ground, Real Part (elan) 1

1 In the Model Builder window, under Results right-click Impedance vs Ground,
Real Part (elan) and choose Duplicate.
2 In the Settings window for 1D Plot Group, type Impedance vs Ground, Absolute
Value in the Label text field.
Global 1
1 In the Model Builder window, expand the Results>Impedance vs Ground, Absolute Value
node, then click Global 1.

abs(conj(elan.Zvsgrnd_els1)) Ω*m^2 Impedance vs Ground,
Absolute Value
4 On the Impedance vs Ground, Absolute Value toolbar, click Plot.
Impedance vs Ground, Absolute Value 1

1 In the Model Builder window, under Results right-click Impedance vs Ground,
Absolute Value and choose Duplicate.
2 In the Settings window for 1D Plot Group, type Impedance vs Ground, Phase Angle
in the Label text field.

Global 1
1 In the Model Builder window, expand the Results>Impedance vs Ground, Phase Angle
node, then click Global 1.

arg(elan.Zvsgrnd_els1) rad Impedance vs Ground, Phase
Angle
4 On the Impedance vs Ground, Phase Angle toolbar, click Plot.

Voltammetry at a Microdisk Electrode
Introduction
Cyclic voltammetry is a common electroanalytical technique. Since the 1980s, it has been
common in voltammetry to use a microdisk electrode as the working electrode (Ref. 1).
This is a disk electrode with a radius of the order of microns, embedded in an insulator
whose surface is flush with the electrode.
Electrolyte
Symmetry
axis
Electrode Insulator
Figure 1: Schematic of the simulation geometry for a microdisk electrode.
These very small electrodes have advantageous mass transport properties that can
maximize the measured current density, and so enable the study of electrochemical
behavior that would not be observable by conventional voltammetry as performed on a
large macroelectrode (See the model Cyclic Voltammetry at a Macroelectrode in 1D.)
This example demonstrates the use of a common approximation in which an electrode

with microscale dimensions is assumed to have stationary (equilibrium) diffusion
properties on the timescale of a voltammetry study. This simplifies the analysis because a
time-dependent model is not required. Instead, a Parametric Sweep is used to assemble a
voltammogram under a quasi-static approximation.
Model Definition
The model contains a 2D axisymmetric domain surrounded by a concentric region in
which Infinite Elements are used to extend the bulk solution in the model to ‘infinity’. The
2 | VO L T A M M E T R Y A T A M I C R O D I S K E L E C T R O D E
approximation that the bulk solution is infinitely distant is suitable if the electrochemical
cell is several orders of magnitude larger than the electrode.
The z = 0 axis is divided by a point at the electrode radius, re, which equals 10 μm. At
r < re, this axis represents the working electrode (microdisk) where the electrochemical
reaction takes place. At r > re, this axis represents the surrounding insulator in-plane with
the disk electrode.
assume that the electrolyte potential φl = 0 (Ref. 2).
The Electroanalysis interface implements chemical species transport equations for the
reactant and product species of the redox couple subject to this assumption. The domain
equation is the diffusion equation (also known as Fick’s 2nd law), which describes the
chemical transport of the electroactive species A and B. At steady-state, this reduces to:
∇ ⋅ ( D i ∇c i ) = 0
At the bulk boundary ( r → ∞ ), we assume a uniform concentration equal to the bulk
concentration for the reactant. The product has zero concentration here, as in bulk.
At the insulating (inert) surface, the normal flux of both species A and B equals zero, since
this surface is impermeable and neither species reacts there.
At the electrode boundary, the reactant species A oxidizes (loses one electron) to form the
product B. By convention, electrochemical reactions are written in the reductive direction:
–
B+e ↔A
1 for A, the “product” in the reductive direction. This formulation is consistent even in
examples such as this model where at certain applied potentials, the reaction proceeds
favorably to convert A to B. The number of electrons transferred, n, equals one.
i loc = nFk 0  c A exp  ---------------------------- – c B exp  ----------------- 
  RT   RT  
coefficient, and η is the overpotential at the working electrode.
ν i i loc
– n ⋅ N i = -------------
nF
The total current recorded at the disk electrode can be extracted by integrating the local
current density across the electrode surface. It is not sufficient to simply multiply by the
area of the electrode, because the current density may be non-uniform. An Integral
Component Coupling is used to define an electrode current variable according to:
I el =  iloc dA
S
S TAT I O N A RY S T U DY
In contrast to macroelectrode voltammetry, a voltammogram recorded at a microdisk does
not exhibit hysteresis. Diffusion is so fast on the timescale of the experiment that a
stationary approximation is suitable. A quasi-static approximation applies when:
2
re
------- « RT
--------
D Fv
where v is the voltammetric scan rate (SI unit: V/s). The two terms in this inequality are
respectively the diffusive and voltammetric timescales of the system.
Within the Stationary study, a parametric sweep is used to study the range of applied
potentials achieved in the voltammogram.

The stationary concentration profile around a microdisk electrode (Figure 2) has a distinct
shape. At large distances from the electrode, the concentration profile is roughly
hemispherical, but close to the disk edge the flux is elevated. For fast kinetics the
concentrations on the electrode surface are roughly equilibrated and so are uniform. This
leads to unequal flux over the surface of the electrode — it is nonuniformly accessible.
Figure 2: Characteristic concentration profile for transport-controlled oxidation of species A

at a microdisk electrode (2D cross section).
The shape of the cyclic voltammogram (Figure 3) illustrates the relation between electrode
kinetics and chemical species transport (diffusion).
Figure 3: Quasi-static (steady-state) cyclic voltammetry recorded at a microdisk electrode. We
can here see the limiting current density as explained below.
Initially, at reducing potentials, the oxidation reaction is not driven, and negligible current
is drawn. As the potential moves towards the reduction potential of the redox couple (0
V), the oxidation reaction is accelerated and the current increases.
Once the oxidation reaction is fast enough that it consumes significant reactant at the
electrode surface, the current becomes limited by the rate of transport of A towards the
working electrode. Because the diffusion layer is equilibrated, this transport-limited
current is constant in time, and independent of applied potential. The analytical Saito
equation gives this limiting current as (Ref. 3):
I lim = 4nFcDr e
where c is the bulk concentration of reactant.
Negative current is never observed for the “steady-state” voltammetry at a microdisk

electrode, since the product species is effectively dispersed to bulk solution. Rapid
diffusion on the voltammetric timescale ensures equilibration between the bulk and the
electrode surface. Because of the absence of product in bulk, this equilibrium means that
the reaction is always oxidative.
Notes About the COMSOL Implementation
A refined mesh is required close to the electrode surface in order to accurately resolve the
concentration profile, and hence the current. The mesh is refined further close to the
singularity where the electrode and insulator boundaries meet. In the Infinite Element
Domain, a Swept mesh is used.
Figure 4: Customized mesh used for the microdisk analysis.
References
1. R.G. Compton and C.E. Banks, Understanding Voltammetry, 2nd ed., London, 2011.

Applications, 2nd ed., Hoboken, 2001.
3. Y. Saito, Review of Polarography (Japan), vol. 15, pp. 177-187, 1968.

microdisk_voltammetry
NEW
MODEL WIZARD
1 In the Model Wizard window, click 2D Axisymmetric.
3 Click Add.
cRed
cOx
5 Click Study.
7 Click Done.
GLOBAL DEFINITIONS
Parameters
microdisk_voltammetry_parameters.txt.
GEOMETRY 1
Draw the model geometry as a quarter circle, and specify the electrode disk radius using a
point.
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 r_max.
4 In the Sector angle text field, type 90.
Point 1 (pt1)
1 On the Geometry toolbar, click Primitives and choose Point.
2 In the Settings window for Point, locate the Point section.
3 In the r text field, type re.
Circle 1 (c1)
Add a second circle that will be used to set up an Infinite Element domain.
Circle 2 (c2)
1 In the Model Builder window, under Component 1 (comp1)>Geometry 1 right-click
Circle 1 (c1) and choose Duplicate.
2 In the Settings window for Circle, locate the Size and Shape section.
3 In the Radius text field, type r_max*1.2.
Your finalized geometry should now like this:
DEFINITIONS
Add an Infinite Element domain, and assign it to the outer domain.
Infinite Element Domain 1 (ie1)
1 On the Definitions toolbar, click Infinite Element Domain.
Now start setting up the physics. Start with the diffusion coefficients.

3 In the DcRed text field, type D1.
4 In the DcOx text field, type D2.
Electrode Surface 1
Add an Electrode Surface boundary node. Set up the electrode kinetics in the Electrode
Reaction subnode.

3 From the Boundary condition list, choose Electrode potential.
4 In the Evsref text field, type E_appl.
2 In the Settings window for Electrode Reaction, locate the Equilibrium Potential section.
3 In the Eeq text field, type Ef.
4 Locate the Electrode Kinetics section. In the k0 text field, type k0.
5 Locate the Stoichiometric Coefficients section. In the νcRed text field, type 1.
6 In the νcOx text field, type -1.
Concentration 1
Specify the bulk composition at the outer boundary.

4 Select the Species cRed check box.
5 In the c0,cRed text field, type c_bulk.
6 Select the Species cOx check box.
Initial Values 1
Initial Values 1.
3 In the cRed text field, type c_bulk.
MESH 1
Edit the default mesh to ensure good numerical accuracy.
Size
3 From the Predefined list, choose Finer.
4 Click to expand the Element size parameters section. Locate the Element Size Parameters
section. In the Maximum element growth rate text field, type 1.1.
Free Triangular 1
1 In the Model Builder window, under Component 1 (comp1)>Mesh 1 click
Free Triangular 1.
2 In the Settings window for Free Triangular, locate the Domain Selection section.
Size 1
1 Right-click Component 1 (comp1)>Mesh 1>Free Triangular 1 and choose Size.
3 From the Geometric entity level list, choose Point.
7 In the associated text field, type re/100.
Mapped 1
1 In the Model Builder window, right-click Mesh 1 and choose Mapped.
2 In the Settings window for Mapped, locate the Domain Selection section.
STUDY 1
The problem is now ready for solving. Simulate a voltammogram by using a Parametric
Sweep for a range of applied potentials.
Parametric Sweep
3 Click Add.

E_appl range(E_start,E_step,E_vertex)
RESULTS
Two default concentration plots are created by default: one in 2D and one revolved 3D
plot.
Concentration, 3D (elan)
Click the Zoom Extents button on the Graphics toolbar.
1D Plot Group 3
Create a plot of the voltammogram as follows.
Global 1
2 In the Model Builder window, right-click 1D Plot Group 3 and choose Global.
3 In the Settings window for Global, click Replace Expression in the upper-right corner of
the y-axis data section. From the menu, choose Component 1>Electroanalysis>
Electrode kinetics>elan.Itot_els1 - Total current.
Orange Battery
Introduction
This tutorial example serves as an introduction to electrochemistry modeling in
COMSOL. The example simulates the currents and the concentration of dissolved metal
ions in a battery (corrosion cell) made from an orange and two metal nails.
Metal nails
Orange
Figure 1: Modeled geometry. Orange and two metal nails. (Due to the high conductivity of the
metal nails, only the orange pulp is included in the computational domain.)
This type of battery is commonly used in chemistry class demonstrations. Instead of an

orange, also lemons or potatoes can be used.
Model Definition
The citric acid and various other ions in the orange serves as electrolyte, and using nails of
different metals as electrodes creates a galvanic potential over the cell.
In this example a zinc nail is used as one of the electrodes, giving rise to the following
electrode reaction:
2+ -
Zn ( s ) → Zn + 2e E eq, 0 = – 0.76 V
The other nail consists of copper, and here hydrogen evolution is assumed to take place:
+ -
2H + 2e → H 2 ( g ) E eq, 0 = 0 V
2 | ORANGE BATTERY
Eeq,0 above denotes the equilibrium potentials at standard conditions versus a standard
hydrogen electrode (SHE). In the model, the equilibrium potentials are corrected for the
pH and zinc concentration of the orange pulp using the Nernst equation.
The model for the currents in the orange and electrodes is set up using the Secondary
Current Distribution interface. The electrolyte current in the orange is thereby solved for
by Ohms law. The conductivity of the metal nails is so high that the electrode domains are
not included in the model, instead boundary conditions on the nail surfaces are used to
set the nail potentials. One nail is grounded and the other one is set to a cell potential to
comply with a total current condition. This would correspond to a situation where the cell
is controlled galvanostatically, for instance by the use of a potentiostat.
Butler-Volmer type expressions, with concentration dependent exchange current density

for the zinc reaction, are used for the electrode kinetics on the surface of the nails within
the orange.
The initial values electrolyte potential is set to correspond to the potential of a cell at open
circuit (that is, no activation potential). Following the definition of the overpotential:
η = φ s – φ l – E eq
the initial value becomes:
φ l, init = φ s – E eq – η = 0 – E eq, Zn – 0 = – E eq, Zn
In an extension of the model, the diffusion and migration of the dissolved zinc ions in the
orange from the zinc electrode reaction is modeled by the Transport of Diluted Species
interface in a time-dependent simulation. This assumes that the zinc ion transport can be
described by the Nernst-Planck equations (without an electroneutrality condition due to
a supporting electrolyte). In addition, the zinc electrode kinetics are modified to be
dependent on the zinc concentration, which increases in the orange as more and more zinc
is dissolved.
The zinc concentration is set to 0.001 mol/m3 at the start of the simulation. All
boundaries except the zinc electrode are insulated.

Figure 2 shows the potential field in the orange. The potential decreases as the current
flows from the zinc electrode (left) to the upper electrode (right). The main part of the
cell voltage loss is due to Ohmic losses in the electrolyte.
3 | ORANGE BATTERY
The performance of the battery could probably be increased by using an electrolyte of
higher conductivity (for example, a lemon instead of an orange) or by decreasing the
distance between the nails.
Figure 2: Potential field in the electrolyte at t=0.
4 | ORANGE BATTERY
Figure 3 shows a polarization plot as the total current of the battery increases from 0 to
1 mA. The large change in cell voltage seen at low currents is due to overpotential losses
at the zinc electrode. Increasing the area of the zinc electrode would decrease this effect.
Figure 3: Polarization plot for the initial concentrations.
Figure 4 shows an isosurface for the 0.2 mol/m3 concentration level of zinc ions after
running the battery for five minutes. Figure 5 shows the how far the 0.2 mol/m3
isosurface level has reached after one hour.
5 | ORANGE BATTERY
Figure 4: 0.2 mol/m3 zinc concentration isosurface after five minutes.
6 | ORANGE BATTERY
Figure 5: 0.2 mol/m3 zinc concentration isosurface after one hour.
Figure 6 shows how the cell current evolves with time. Due to the increase of zinc ions at
the zinc nail electrode, the battery current decreases for a constant cell current.
7 | ORANGE BATTERY
Figure 6: Cell current vs. time.
Suggested Exercises and Extensions of the Model

Change the radius of the nails and the value of the electrolyte conductivity and investigate
how this affects the polarization plot.
The hydrogen concentration is not included in the model. Add an additional

concentration under Dependent Variables on the Transport of Diluted Species node to
monitor the change in pH of the cell then couple the flux of hydrogen ions on the copper
surface by using an additional Electrode-Electrolyte Interface Coupling node.
The dissolved zinc ions may form a layer of zinc hydroxide on the zinc surface, giving rise
to an additional potential drop. You may use the Film Resistance section on the Electrode
Surface node to include this potential drop. The value of the film resistance could for
instance be a function of the zinc ion concentration variable in the pulp. Alternatively you
may add a Surface Reactions interface to model the buildup of the surface concentration
of zinc hydroxide, and then couple the film resistance to the hydroxide concentration.
8 | ORANGE BATTERY
Application Library path: Electrochemistry_Module/Tutorials/orange_battery
NEW
MODEL WIZARD
3 Click Add.
4 Click Study.
6 Click Done.
GEOMETRY 1
Start by drawing the geometry; one sphere (the orange) and two cylinders (the metal
nails).
Sphere 1 (sph1)
1 On the Geometry toolbar, click Sphere.
2 In the Settings window for Sphere, locate the Size section.
3 In the Radius text field, type 5e-2.
Cylinder 1 (cyl1)
1 On the Geometry toolbar, click Cylinder.
2 In the Settings window for Cylinder, type Zinc nail in the Label text field.
3 Locate the Size and Shape section. In the Radius text field, type 2e-3.
4 In the Height text field, type 5e-2.
5 Locate the Position section. In the x text field, type -2e-2.
9 | ORANGE BATTERY
6 In the z text field, type 2e-2.
By enabling Resulting objects selection you can easily select all boundaries of the nail later
on when setting up the physics.
7 Locate the Selections of Resulting Entities section. Select the Resulting objects selection
check box.
8 From the Show in physics list, choose All levels.
Duplicate the cylinder and change the x position to draw the second nail.
Zinc nail 1 (cyl2)

1 Right-click Zinc nail and choose Duplicate.
2 In the Settings window for Cylinder, type Copper nail in the Label text field.
3 Locate the Position section. In the x text field, type 2e-2.
GLOBAL DEFINITIONS
Load some global parameters from a file. These will be used in multiple places in the
model.
Parameters
orange_battery_parameters.txt.
DEFINITIONS
Load also some variable definitions from a file.
Variables 1
1 In the Model Builder window, under Component 1 (comp1) right-click Definitions and
choose Variables.
orange_battery_variables.txt.

Now, start setting up the current distribution model.
10 | ORANGE BATTERY
Change the selection of the entire physics interface to the orange domain only.
1 In the Model Builder window, click Secondary Current Distribution (cd).

Also create a selection for the orange domain. This will facilitate if the geometry needs
to be changed in the future. Selections is generally a convenient way to group different
parts of the geometry together.
3 In the Settings window for Secondary Current Distribution, locate the Domain Selection
section.
4 Click Create Selection.
5 In the Create Selection dialog box, type Orange in the Selection name text field.
6 Click OK.
Electrolyte 1
An Electrolyte node has already been added to the model by default. The selection is
locked to all selected domains of the physics interface, which in this case is the orange only.
Set the electrolyte conductivity.

Secondary Current Distribution (cd) click Electrolyte 1.
2 In the Settings window for Electrolyte, locate the Electrolyte section.
3 From the σl list, choose User defined. In the associated text field, type sigma.
Electrode Surface 1
Use Electrode Surface nodes to define both a metal electrode potential and an electrode-
electrolyte interface. Use a Bulter-Volmer expression for the zinc electrode. The hydrogen
kinetics are assumed to be very fast so that a linearized Butler-Volmer expression is
applicable.

2 In the Settings window for Electrode Surface, locate the Boundary Selection section.
3 From the Selection list, choose Zinc nail.
Enable transparency and inspect the active boundaries in the graphics window.
4 Click the Transparency button on the Graphics toolbar.
11 | ORANGE BATTERY
4 Locate the Equilibrium Potential section. In the Eeq text field, type E_eq_Zn.
Butler-Volmer.
6 In the αa text field, type alpha_a_Zn.
7 In the αc text field, type alpha_c_Zn.
8 In the i0 text field, type i0_Zn.
Electrode Surface 2
Now define the copper electrode in a similar way. First add a parameter for the total
current. This parameter will also be used in the study to perform a galvanic polarization
sweep over the cell.

3 From the Selection list, choose Copper nail.
4 Locate the Boundary Condition section. From the Boundary condition list, choose
Total current.
5 In the Il, total text field, type -i_app.
4 Locate the Equilibrium Potential section. In the Eeq text field, type E_eq_H2.
5 Locate the Electrode Kinetics section. In the i0 text field, type i0_H2.
Initial Values 1
We are using non-linear kinetics in the model. Provide an initial value for the electrolyte
potential in order to reduce solver time and improve convergence. As a rule of thumb one
can often use the negative of the equilibrium potential of the grounded electrode as initial
value for the electrolyte potential.

Secondary Current Distribution (cd) click Initial Values 1.
12 | ORANGE BATTERY
3 In the phil text field, type -E_eq_Zn0.
STUDY 1
Since we are using the default mesh settings, the model is now ready for solving.
RESULTS
Electrolyte Potential (cd)

Plots of the electrolyte potentials are created by default.
Use an isosurface for visualizing the potential field in the electrolyte.
3D Plot Group 5
2 In the Settings window for 3D Plot Group, type Potential Isosurface in the Label text
field.
Isosurface 1
1 Right-click Potential Isosurface and choose Isosurface.
2 In the Settings window for Isosurface, locate the Levels section.
3 In the Total levels text field, type 25.
4 On the Potential Isosurface toolbar, click Plot.
Compare with Figure 2 in the Results and Discussion section.
STUDY 1
Step 1: Stationary
Now use an Auxiliary Sweep to solve over a range of cell currents in order to create a
polarization plot.

4 Click Add.
13 | ORANGE BATTERY

i_app (Applied Current) 0 10^range(-5,0.2,-3) A
RESULTS
Create a polarization plot as follows:
1D Plot Group 6
2 In the Settings window for 1D Plot Group, type Polarization Plot in the Label text
field.
Global 1
1 Right-click Polarization Plot and choose Global.
2 In the Settings window for Global, click Replace Expression in the upper-right corner of
the y-axis data section. From the menu, choose Component 1>
Secondary Current Distribution>cd.phis_eebii2 - Electric potential.
3 On the Polarization Plot toolbar, click Plot.
COMPONENT 1 (COMP1)
Now, extend the model to investigate the battery voltage over time at a certain load
current. Start by adding a physics interface to handle the mass transport of zinc ions.
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 tree, select Chemical Species Transport>Transport of Diluted Species (tds).
4 Click Add to Component in the window toolbar.
5 On the Home toolbar, click Add Physics to close the Add Physics window.
1 In the Settings window for Transport of Diluted Species, locate the Domain Selection
section.
14 | ORANGE BATTERY
2 From the Selection list, choose Orange.
The orange pulp is quiescent so convection can be ignored in the model.
3 Locate the Transport Mechanisms section. Clear the Convection check box.
(Due to the presence of a lot of other ions in the pulp, acting as supporting electrolyte,
we assume the potential gradients to be small and hence also ignore the effect of
migrative transport of the zinc ions.)
Electrode Surface Coupling 1

For this example we will use the default diffusion coefficient value in the Tranpsort
Properties node so no settings are needed on the default domain node. The following steps
couple the electrochemical reaction currents to the ion flux at the electrode surface:
1 On the Physics toolbar, click Boundaries and choose Electrode Surface Coupling.
3 In the Settings window for Electrode Surface Coupling, locate the Boundary Selection
section.
4 From the Selection list, choose Zinc nail.
Reaction Coefficients 1
1 In the Model Builder window, expand the Electrode Surface 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, Electrode Reaction 1 (cd/eebii1/er1).
4 Locate the Stoichiometric Coefficients section. In the n text field, type 2.
5 In the νc text field, type -1.
The stochiometric number refers to the stochiometry number of the reacting species
when written as a reduction reaction.
Initial Values 1
Set the initial zinc ion concentration at the start of the time-dependent simulation.

3 In the c text field, type c_Zn20.
15 | ORANGE BATTERY
DEFINITIONS
The zinc ion concentration is no longer constant. Modify the equilibrium potential and
exchange current density variables for the zinc electrode to be dependent on the local
concentration of zinc ions. The name of this variable is c by default in the Transport of
Diluted Species interface.
Variables 1
1 In the Model Builder window, under Component 1 (comp1)>Definitions click Variables 1.

c_Zn2 c mol/m³ Zinc ion concentration (used in
above expressions)
ROOT
Create a new time-dependent study for the concentration simulation.
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>
Time Dependent with Initialization.
4 Click Add Study in the window toolbar.
5 On the Home toolbar, click Add Study to close the Add Study window.
STUDY 2
Step 1: Current Distribution Initialization

Use a secondary current distribution during the initialization step.
1 In the Settings window for Current Distribution Initialization, locate the Study Settings
section.
2 From the Current distribution type list, choose Secondary.
Step 2: Time Dependent

1 In the Model Builder window, under Study 2 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(0,60,3600).
16 | ORANGE BATTERY
RESULTS
Boundary Electrode Potential vs Ground (cd)

A plot for how the cell potential changes with time is created by default.
1 In the Model Builder window, under Results click

Boundary Electrode Potential vs Ground (cd).
2 In the Settings window for 1D Plot Group, type Cell Potential vs Time in the Label
text field.
3 On the Cell Potential vs Time toolbar, click Plot.
Plot the zinc concentration in the orange as follows:
3D Plot Group 14
2 In the Settings window for 3D Plot Group, type Concentration Isosurface in the
Label text field.
3 Locate the Data section. From the Data set list, choose Study 2/Solution 2 (sol2).
4 From the Time (s) list, choose 240.
Isosurface 1
1 Right-click Concentration Isosurface and choose Isosurface.
2 In the Settings window for Isosurface, click Replace Expression in the upper-right corner
of the Expression section. From the menu, choose Component 1>
Transport of Diluted Species>c - Concentration.
3 Locate the Levels section. From the Entry method list, choose Levels.
4 In the Levels text field, type 0.2.
5 On the Concentration Isosurface toolbar, click Plot.
Export
The following steps create an animation of the zinc ion isosurface during the simulated
time:
17 | ORANGE BATTERY
Animation 1
1 On the Results toolbar, click Animation and choose File.
2 In the Settings window for Animation, locate the Target section.
3 From the Target list, choose Player.
4 Locate the Scene section. From the Subject list, choose Concentration Isosurface.
5 Locate the Animation Editing section. From the Time selection list, choose From list.
At t=0 there is no concentration gradient in the orange, de-select the first time-step.
6 In the Times (s) list, choose 0 (2), 60, 120, 180, 240, 300, 360, 420, 480, 540, 600, 660,
720, 780, 840, 900, 960, 1020, 1080, 1140, 1200, 1260, 1320, 1380, 1440, 1500, 1560, 1620,
1680, 1740, 1800, 1860, 1920, 1980, 2040, 2100, 2160, 2220, 2280, 2340, 2400, 2460, 2520,
2580, 2640, 2700, 2760, 2820, 2880, 2940, 3000, 3060, 3120, 3180, 3240, 3300, 3360, 3420,
3480, and 3540.
7 Right-click Animation 1 and choose Play.
Compare the last frame at time 3600 s with Figure 5 in the Results and Discussion
section.
STUDY 1
Step 1: Stationary
Note that if you want to experiment with the model by changing parameter values and
simulate new polarization plots using the first (stationary) study, you have to disable the
Transport of Diluted Species interface in that study as follows:

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
18 | ORANGE BATTERY
Thin Layer Chronoamperometry
Introduction
Chronoamperometry is a technique in electroanalysis in which current drawn at an
electrode is measured after a rapid step in the applied voltage.
In a thin-layer cell, the anode and cathode are separated by a microscale distance. This
means that chemical species transport across the cell is fast, so an analyte in the cell can be
consumed exhaustively after only a few seconds. By integrating the current transient
(chronoamperogram), the initial concentration of analyte can be determined.
If the kinetics of the electrochemical reaction are always fast, there is no need to resolve
the current density as a function of applied potential. Instead, the concentration of the
analyte can be assumed to be driven to zero at the working electrode surface. Under this
approximation, only the chemical species transport needs to be resolved.
Model Definition
This model contains a single 1D domain of length L = 60 μm, which is the thickness of
the thin layer. Transport in plane with the anode and cathode is ignored; only normal
transport is considered, which is assumed to be uniform across the cell.
The transport of the analyte obeys the diffusion equation (Fick’s 2nd Law):
∂----c-
= ∇ ⋅ ( D ∇c )
∂t
The solution is assumed to be static (“quiescent”) so there is no mass transport by

convection. A supporting electrolyte is present in high concentration, so the electric field
is also taken to be zero. We do not model the product species as its concentration does not
influence the current density.
A high overpotential is applied so that the analyte undergoes a very fast electrochemical
reaction at the working electrode surface (x = 0). To model this, the analyte concentration
here is rapidly stepped to zero. The facing surface (x = L), is impermeable to the analyte—
no flux is passed. We assume the counter reaction of the electrochemical cell to either take
place at a physically separate counter electrode, or to involve a distinct chemical species,
present in excess, which we ignore in this model.
2 | THIN LAYER CHRONOAMPEROMETR Y

T I M E - D E P E N D E N T S T U DY
The Einstein equation gives the time for the mean position of a diffusion layer to cross a
distance L, as a function of the diffusion coefficient D:
2
L
t = --------
4D
In the thin layer, the Einstein time is 0.9 s. After a few Einstein times, the analyte reacts to
near exhaustion, and so the duration of the simulation is set to 5 s.

The concentration profiles through time demonstrate the growth of the diffusion layer
across the cell (Figure 1).
Figure 1: Concentration profiles of the analyte across the thickness of the cell, as the experiment
proceeds (top-left to bottom-right)
Once the diffusion layer encounters the outer boundary of the cell, the concentration here
begins to diminish as the continuing electrochemical reaction exhausts the available
analyte.

As the diffusion layer expands, the flux at the working electrode becomes smaller.
Correspondingly the current also decreases (Figure 2).
Figure 2: Measured chronoamperogram for the thin-layer cell
From transport theory, the chronoamperometric current for an infinite expanse of bulk
solution falls off inversely proportionally to the square root of time, as given by the Cottrell
equation, where i is the current density, n is the number of electrons transferred per
molecule of analyte, c is the bulk concentration of analyte and D is its diffusion coefficient:
D-
i = nFc ----
πt

Figure 3: Simulated chronoamperogram compared on a logarithmic scale to the Cottrell
equation for chronoamperometry with unlimited available analyte. The deviation at long
times is caused by the finite quantity of analyte the cell.
By comparing the simulated results with the Cottrell equation, plotted on a logarithmic
scale (Figure 3), good agreement is observed until roughly t = 1 s. At this time—which is
approximately the Einstein time noted above—the diffusion layer encounters the wall of
the cell.
After this point, the current diminishes more quickly due to the exhaustion of available
electroactive material for reaction. Under these conditions, the Cottrell equation no
longer applies—the simulated current deviates negatively.
By integrating the concentration across the cell, we can calculate the proportion of the
initial amount of analyte that has been consumed (Figure 4). After 5 seconds, 99% of the
analyte has undergone an electrochemical reaction.

Figure 4: Proportion of the initial quantity of analyte that is consumed through the
experiment
References
1. R.G. Compton and C.E. Banks, Understanding Voltammetry, 2nd ed., World
Scientific Publishing Co. Pte. Ltd, London, 2011.

Applications, 2nd ed., Wiley, Hoboken, 2001.
3. F.G. Cottrell, Zeitschrift für Physikalische Chemie, vol. 42, pp. 385–431, 1903.

thin_layer_chronoamperometry

NEW
MODEL WIZARD
3 Click Add.
6 Click Study.
7 In the Select Study tree, select Preset Studies>Time Dependent.
8 Click Done.
GLOBAL DEFINITIONS
Add the model parameters from a text file.
Parameters
thin_layer_chronoamperometry_parameters.txt.
GEOMETRY 1
Create the model geometry as a single interval.
Interval 1 (i1)
3 In the Right endpoint text field, type L.
DEFINITIONS
Add a smoothed step function that will be used to step the concentration at the electrode
from initial conditions to zero as a continuous function of time.

Step 1 (step1)
1 On the Home toolbar, click Functions and choose Local>Step.
2 In the Settings window for Step, locate the Parameters section.
3 In the Location text field, type 0.5.
4 Click to expand the Smoothing section. In the Size of transition zone text field, type 1.
Variables 1
Add some variables that will be used during postprocessing for comparing the simulated
current with the Cottrell equation.
1 On the Home toolbar, click Variables and choose Local Variables.


i_el -F_const*A_el* A Total Current
elan.tflux_cx
i_Cottrell F_const*A_el*c_bulk* A Cottrell equation
sqrt(D/(pi*t+eps)) current
Now start setting up the physics. Start with the domain settings for the diffusion
coefficient and the initial concentration.

3 In the Dc text field, type D.
Initial Values 1
Initial Values 1.
3 In the c text field, type c_bulk.
Concentration 1
Set up the Concentration condition on the boundary using the step function defined
above.

4 Select the Species c check box.
5 In the c0,c text field, type c_bulk*(1-step1(t/t_rise)).
MESH 1
Refine the default mesh.
Size
Size 1
choose Size.
7 In the associated text field, type x_step/5.
Edge 1
1 In the Model Builder window, under Component 1 (comp1)>Mesh 1 click Edge 1.

2 In the Settings window for Edge, click Build Selected.
Your finished mesh should now look like this:
STUDY 1

Your model is now ready for solving. Solve for a time range of 5 s.
2 In the Times text field, type range(0,0.1,5).
RESULTS
The first default plot group shows the concentration.
Create the chronoamperogram as follows:
Point Graph 1
2 In the Model Builder window, right-click 1D Plot Group 2 and choose Point Graph.
10 | THIN LAYER CHRONOAMPEROMETRY

5 In the Expression text field, type i_el.
1D Plot Group 2
2 In the Settings window for 1D Plot Group, type Chronoamperogram in the Label text
field.
3 Click to expand the Axis section. Select the Manual axis limits check box.
4 In the x minimum text field, type 0.1.
5 In the x maximum text field, type 5.
6 In the y minimum text field, type 0.
7 In the y maximum text field, type 5e-6.
8 On the Chronoamperogram toolbar, click Plot.
Now, duplicate the chronoamperogram and compare, in log scale, the simulated curve
to the Cottrell equation.
Chronoamperogram 1
1 Right-click Results>Chronoamperogram and choose Duplicate.
2 In the Settings window for 1D Plot Group, type Comparison to Cottrell equation
in the Label text field.
Comparison to Cottrell equation

1 Right-click Results>Comparison to Cottrell equation and choose Global.

i_Cottrell A Cottrell equation current
4 In the Model Builder window, expand the Results>Comparison to Cottrell equation node,
then click Comparison to Cottrell equation.
5 In the Settings window for 1D Plot Group, locate the Axis section.
6 Clear the Manual axis limits check box.
7 Select the x-axis log scale check box.
8 Select the y-axis log scale check box.
9 On the Comparison to Cottrell equation toolbar, click Plot.
10 Click to expand the Axis section. Select the Manual axis limits check box.

11 In the x minimum text field, type 1e-5.
12 On the Comparison to Cottrell equation toolbar, click Plot.
Derived Values
Finally, plot the extent of reaction by calculating the average amount of reacted
concentration in a table, and then plotting the table data.
Line Average 1
1 On the Results toolbar, click More Derived Values and choose Average>Line Average.
2 Click in the Graphics window and then press Ctrl+A to select all domains.
3 In the Settings window for Line Average, locate the Expressions section.

(c_bulk-c)/c_bulk 1 Extent of reaction
5 Click New Table.
TABLE
1 Go to the Table window.
2 Click Table Graph in the window toolbar.
RESULTS
1D Plot Group 4
2 In the Settings window for 1D Plot Group, type Extent of reaction in the Label text
field.
12 | THIN LAYER CHRONOAMPEROMETRY

Electrochemical Treatment of Tumors
Introduction
The electrochemical treatment of tumors implies that diseased tissue is treated with direct
current through the use of metallic electrodes inserted in the tumor. When tissue is
electrolyzed, two competing reactions take place at the anode: oxygen evolution and
chlorine production. The oxygen-evolution reaction also produces H+ ions, which lower
the pH close to the anode. It should be stressed that chlorine production also leads to
lowered pH through the hydrolysis of chlorine. One effect of low pH is the permanent
destruction of hemoglobin in the tissue, which results in destruction of tumor tissue.
- -
2Cl = Cl 2 ( g ) + 2e
(1)
+ -
2H 2 O = 4H + O 2 ( g ) + 4e
One challenge in developing this method of cancer treatment is in predicting the doses
required for tumor destruction. One possible tool for dose planning is by modeling the
reactions that take place close to the electrodes.
This example presents a first simple model for the development of dose-planning methods.
More advanced models for dose planning, including secondary effects of chlorine, are
found in Ref. 1, which also presents and solves models for the cathode.
Model Definition
This model uses the Tertiary Current Distribution, Nernst-Planck interface to predict the
transport and reaction in the electrolysis of tumor tissue in a liver. A needle electrode is
placed in the tumor, and transport is assumed to take place radially to and from this
electrode. Because you can assume rotational symmetry, the computational domain
reduces to a line (ra, rr) where ra is 1 mm and rr is 6 cm (see Figure 1).
The species you consider in the model are the protons, chloride, and sodium. At the
surface of the anode you account for the chlorine and oxygen evolution reactions; see
2 | E L E C T R O C H E M I C A L TR E A T M E N T O F TU M O R S
Equation 1.
Anode
Computational domain
Figure 1: Diagram of the cylindrical modeling domain inside a tumor.
This simplified model considers only a 1D model of the transport between two points, that
is, between the two electrodes. The material balance for the species i is given by
∂c
-------i + ∇ ⋅ ( – D i ∇c i – z i u mi Fc i ∇φ l ) = R i
∂t
where ci is the concentration (SI unit: mol/m3), Di give the diffusivities (SI unit: m2/s),
zi equals the charge, umi represents the mobility (SI unit: (mol·m2)/(J· s)), and Ri is the
production term for species i (SI unit: mol/(m3·s)), F denotes Faraday’s constant (SI unit:
C/mol), and φl is the electrolyte potential (SI unit: V). The mobility, umi, can be
expressed in terms of Di, R, and T as
Di
u mi = --------
RT
The conservation of electric charge is obtained through the divergence of the current
density:
 N 
∇ ⋅  F z i ( – D i ∇c i – z i u mi Fc i ∇φ l ) = 0
2
 i=1 
At the electrode surface (r = ra) you use the Electrode Surface boundary node to specify
the electrode reactions and the resulting fluxes for the ionic species that are included in the
electrode reactions, H+ and Cl-. For the inert ionic species, Na+, the transport through
the electrode surface equals zero. The expressions for molar fluxes at the boundary are
based on the electrode reaction currents according to
ν ij j j
N i ⋅ n = -----------
nj F
where Ni is the flux, νij represents the stoichiometric coefficient for the ionic species i in
reaction j, and nj is the number of electrons in reaction j.
You can express the current densities for the two reactions using the Electrode Reaction
nodes with Concentration Dependent Kinetics expressions. Introducing dimensionless
pressure, P = p/pb, and concentration, C = c/cb, (where b denotes the reference
concentration), the current density for the oxygen evolution is
Fη I Fη
------------I
 – ------------
2RT 1⁄4 2RT 
j I = j I, 0  e – ( P O2 ) CH + e 
 
where jI0, is the exchange current density (SI unit: A/m2) and ηI is the overpotential for
the oxygen evolution reaction, defined as
η I = φ s – φ l – E eq, I
where Eeq,I (SI unit: V) is the equilibrium potential for the oxygen evolution reaction.
The chlorine evolution reaction is similarly given by the expression
Fη II Fη II
 – ------------
2RT 1 ⁄ 2 2RT 
------------
j II = j II, 0  C Cl – e – ( P Cl2 ) e 
 
Using the input values nI = nI = 1, νH,I = 1, and νCl,II = −1, gives the fluxes at the electrode
surface:
jI
N H ⋅ n = ----
F
j II
N Cl ⋅ n = – ------
F
At the exterior boundary, assume the concentration is constant, ci = ci0, and set the
potential to
V 0 ( t ) = –  0.4977 + 0.2567 ⋅ ln  100 + ------  V

t
  1 s 
where t denotes time.
The initial concentration is constant: ci = ci0. You obtain the initial potential profile from
the solution of the domain equations and boundary conditions at t = 0, yielding
j ra0 r a ra
V ( t = 0 ) = V ra0 + ---------------- log -----
κ0 r
where Vra0 is the potential satisfying jI + jII = j0 and κ0 is the conductivity at t = 0.
The input data is listed in this table:

TABLE 1: INPUT DATA
PARAMETER VALUE DESCRIPTION
DNa 1.33·10-9 m2/s Diffusion coefficient, Na+

DH 9.31·10-9 m2/s Diffusion coefficient, H+
DCl 2.03·10-9 m2/s Diffusion coefficient, Cl-
cNa,0 0.16 mol/liter Inlet concentration, Na+
-7
cH,0 10 mol/liter Inlet concentration, H+
cCl,0 0.16 mol/liter Inlet concentration, Cl-
j0 100 A/m2 Initial current density
-6 2
jI,0 10 A/m Exchange current density, reaction I
jII,0 10 A/m2 Exchange current density, reaction II
Vra,0 -1.4787 V Initial anode potential
Eeq,I 1.23 V Equilibrium potential, reaction I
Eeq,II 1.36 V Equilibrium potential, reaction II
T 298 K Temperature
pO2 1 atm
pCl2 1 atm
The plot in Figure 2 shows the pH for different time steps. You can see that values below
pH 2 are reached somewhere between 1800 and 2400 s. A closer examination reveals that
it occur after 2000 s. At this pH, tumor destruction starts to occur very rapidly according
to the experimental and theoretical findings in Ref. 1.
Figure 2: pH-profiles at different time steps during the treatment.
The corresponding H+ profile in Figure 3 shows that the concentration maximum is not
at the anode surface.
Figure 3: Proton concentration in the domain at different time steps.
This result arises because the current density is not constant over time. At high current
densities, large amounts of protons are produced and this front moves inwards in the
domain as the current density is lowered.
The corresponding plot for chloride (Figure 4) shows a continuous decrease of chloride
concentration close to the anode surface. This in turn decreases the production of chlorine
and increases oxygen evolution.
Figure 4: Chloride concentration at different time steps.
The current-density plot in Figure 5 shows that the total current decreases rapidly as the
concentration overvoltage for chlorine formation increases, due to lowered chloride
concentration at the anode surface. The potential is then increased, which results in an
increase in total current through increased oxygen evolution.
Figure 5: Total current density and current density for the competing reactions on the anode
surface. Oxygen evolution is the lowest graph.
Reference
1. E. Nilsson, Modelling of the Electrochemical Treatment of Tumors, PhD. thesis, Dept.
Chemical Engineering and Technology, Royal Inst. of Technology, Stockholm, Sweden,
2000.

Electrochemical_Engineering/tumor
NEW
MODEL WIZARD
1 In the Model Wizard window, click 1D Axisymmetric.
2 In the Select Physics tree, select Electrochemistry>Tertiary Current Distribution, Nernst-
Planck>Tertiary, Electroneutrality (tcd).
3 Click Add.
Na
H
Cl
6 Click Study.
7 In the Select Study tree, select Preset Studies>Time Dependent.
8 Click Done.
GLOBAL DEFINITIONS
Start by loading the model parameters and variables from text files.
Parameters
tumor_parameters.txt.
DEFINITIONS
Variables 1
1 On the Home toolbar, click Variables and choose Local Variables.
tumor_variables.txt.
GEOMETRY 1
Create the geometry as a single interval.
Interval 1 (i1)
3 In the Left endpoint text field, type r_a.
4 In the Right endpoint text field, type r_ext.
5 Right-click Interval 1 (i1) and choose Build Selected.
TE R T I A R Y C U R R E N T D I S T R I B U T I O N , N E R N S T - P L A N C K ( T C D )
Electrolyte 1
Now start with the physics, begin with the electrolyte settings.

Nernst-Planck (tcd) click Electrolyte 1.
2 In the Settings window for Electrolyte, locate the Model Input section.
4 Locate the Diffusion section. In the DNa text field, type D_Na.
5 In the DH text field, type D_H.
6 In the DCl text field, type D_Cl.
7 Locate the Migration in Electric Field section. In the zNa text field, type z_Na.
8 In the zH text field, type z_H.
9 In the zCl text field, type z_Cl.
Now set the potential of the exterior end, and then the concentration.

3 In the Settings window for Electrolyte Potential, locate the Electrolyte Potential section.
4 In the φl, bnd text field, type V0.
Concentration 1
4 Select the Species H check box.
5 In the c0,H text field, type H0.
6 Select the Species Cl check box.
7 In the c0,Cl text field, type Cl0.
Electrode Surface 1
Now set up the anode, and the anode reactions.

4 Locate the Equilibrium Potential section. In the Eeq text field, type E_eqI.
Concentration dependent kinetics.
6 In the i0 text field, type j_I0.
7 In the CO text field, type H/H0.
8 Locate the Stoichiometric Coefficients section. In the νH text field, type -1.
Electrode Surface 1
In the Model Builder window, under Component 1 (comp1)>Tertiary Current Distribution,
Nernst-Planck (tcd) click Electrode Surface 1.
1 On the Physics toolbar, click Attributes and choose Electrode Reaction.
4 Locate the Equilibrium Potential section. In the Eeq text field, type E_eqII.
Concentration dependent kinetics.
6 In the i0 text field, type j_II0.
7 In the CR text field, type Cl/Cl0.
8 Locate the Stoichiometric Coefficients section. In the νCl text field, type 1.
Initial Values 1
Nernst-Planck (tcd) click Initial Values 1.
3 In the H text field, type H0.
4 In the Cl text field, type Cl0.
5 In the phil text field, type V_init.
MESH 1
Create a user defined mesh with a very fine resolution close to the anode.

3 From the Sequence type list, choose User-controlled mesh.
Size
Size 1
choose Size.
7 In the associated text field, type 1e-8.
8 Select the Maximum element growth rate check box.
9 In the associated text field, type 1.1.
STUDY 1

Modify the default solver to store all steps taken by the solver, and solve the problem.
1 In the Model Builder window, under Study 1 click Step 1: Time Dependent.
3 In the Times text field, type 0 3600.
Solution 1 (sol1)
2 In the Model Builder window, expand the Solution 1 (sol1) node, then click Time-
Dependent Solver 1.
3 In the Settings window for Time-Dependent Solver, click to expand the Output section.
4 From the Times to store list, choose Steps taken by solver.
RESULTS
Concentration (tcd)
The following instructions show how to create the plots shown in Figure 3 to Figure 5.
1 In the Model Builder window, under Results click Concentration (tcd).

2 In the Settings window for 1D Plot Group, type Proton concentration in the Label text
field.
3 Locate the Data section. From the Time selection list, choose Interpolated.
4 In the Times (s) text field, type range(0,600,3600).
Line Graph 1
1 In the Model Builder window, expand the Results>Proton concentration node, then click
Line Graph 1.
2 In the Settings window for Line Graph, click to expand the Legends section.
3 Select the Show legends check box.
Find the Line markers subsection. From the Marker list, choose Cycle.
5 Locate the y-Axis Data section. In the Expression text field, type H.
6 On the Proton concentration toolbar, click Plot.
Compare the plot with that shown in Figure 3.
Proton concentration 1
1 In the Model Builder window, under Results right-click Proton concentration and choose
Duplicate.
2 In the Settings window for 1D Plot Group, type Chloride concentration in the Label
text field.
Line Graph 1
1 In the Model Builder window, expand the Results>Chloride concentration node, then click
Line Graph 1.
3 In the Expression text field, type Cl.
4 On the Chloride concentration toolbar, click Plot.
Compare with the plot in Figure 4.
Chloride concentration 1
1 In the Model Builder window, under Results right-click Chloride concentration and choose
Duplicate.
2 In the Settings window for 1D Plot Group, type pH in the Label text field.
Line Graph 1
1 In the Model Builder window, expand the Results>pH node, then click Line Graph 1.
3 In the Expression text field, type pH.
4 On the pH toolbar, click Plot.
The plot should look like that in Figure 2.
1D Plot Group 5
Finally, reproduce the plot shown in Figure 5.
2 In the Settings window for 1D Plot Group, type Electrode reaction current
densities in the Label text field.
Point Graph 1
1 Right-click Electrode reaction current densities and choose Point Graph.
3 In the Settings window for Point Graph, click Replace Expression in the upper-right
corner of the y-axis data section. From the menu, choose Component 1>
Tertiary Current Distribution, Nernst-Planck>Electrode kinetics>tcd.iloc_er1 -
Local current density.
Legends
Oxygen evolution
Point Graph 2
1 Right-click Results>Electrode reaction current densities>Point Graph 1 and choose
Duplicate.
3 In the Expression text field, type tcd.iloc_er2.
4 Click to expand the Title section. From the Title type list, choose None.
Find the Line style subsection. From the Line list, choose Dash-dot.
Legends
Chlorine evolution
7 On the Electrode reaction current densities toolbar, click Plot.
Point Graph 3
1 Right-click Results>Electrode reaction current densities>Point Graph 2 and choose
Duplicate.
2 In the Settings window for Point Graph, click Replace Expression in the upper-right
corner of the y-axis data section. From the menu, choose Component 1>
Tertiary Current Distribution, Nernst-Planck>Electrode kinetics>tcd.itot -
Total interface current density.
3 Locate the Coloring and Style section. Find the Line style subsection. From the Line list,
choose Dashed.
Legends
Total electrode current density
5 On the Electrode reaction current densities toolbar, click Plot.
Wire Electrode
Introduction
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.
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.
2 | WIRE ELECTRODE
.
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 Faraday
constant (SI unit: As/mol), φ i the ionic potential, and u the velocity vector (SI unit: m/
3 | WIRE ELECTRODE
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:
 –zi mi Fci ∇φl

2
i = –F
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 equivalent to 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
which sets the boundary condition for the cathode.
4 | WIRE ELECTRODE
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
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).
5 | WIRE ELECTRODE
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:
i a = i 0  ----- exp ( η ( 1 – β )F ⁄ ( RT ) ) – exp ( ηβF ⁄ ( RT ) )

c
(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)
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:
6 | WIRE ELECTRODE
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 highest at the
corners of the wires and close to zero at the central parts of the wire structure.
7 | WIRE ELECTRODE
Figure 3: Primary current distribution, Ecell=1.45 V. Potential distribution in the electrolyte
(top) and current density on the anode (bottom).
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
8 | WIRE ELECTRODE
distribution the secondary current distribution is smoother, this is due to the effect that a
high local current density induces local overpotential 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).
9 | WIRE ELECTRODE
TERTIARY CURRENT DSITRIBUTION
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.
10 | WIRE ELECTRODE
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=1.65 V. Potential distribution in the electrolyte

(top) and current density on the anode (bottom).
11 | WIRE ELECTRODE
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.

Electrochemical_Engineering/wire_electrode
NEW
MODEL WIZARD
Primary and Secondary Current Distribution>Primary Current Distribution (cd).
3 Click Add.
4 Click Study.
6 Click Done.
12 | WIRE ELECTRODE
GEOMETRY 1
The model geometry is available as a parameterized geometry sequence in a separate
MPH-file. If you want to build it from scratch, follow the instructions in the section
Appendix — Geometry Modeling Instructions. Otherwise load it from file with the
following steps.
1 On the Geometry toolbar, click Insert Sequence.

wire_electrode_geom_sequence.mph.
GLOBAL DEFINITIONS
Now start defining the physics for the primary current distribution simulation. Begin with
the model parameters.
Parameters
Name Expression Value Description

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
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 Built-In>Water, liquid.
5 On the Home toolbar, click Add Material to close the Add Material window.
13 | WIRE ELECTRODE
MATERIALS
Water, liquid (mat1)


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

4 In the Rename Material dialog box, type Electrolyte in the New label text field.
5 Click OK.
PRIMARY CURRENT DISTRIBUTION (CD)
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.
Electrode Surface 1
Create selections for these anodes. The selection will be used later when setting up more
physics, meshing and post-processing.
5 In the Create Selection dialog box, type Cathodes in the Selection name text field.
6 Click OK.
3 In the Eeq text field, type Eeq_c.
Electrode Surface 2
14 | WIRE ELECTRODE
2 Select Boundaries 6–51 only.
This selection is easiest to achieve by selecting all boundaries (the ’All boundaries’ check
box), followed by deselecting all exterior surfaces.
5 In the Create Selection dialog box, type Anode in the Selection name text field.
6 Click OK.
8 In the φs, ext text field, type Ecell.
3 In the Eeq text field, type Eeq_a.
Initial Values 1
Also, provide initial values for the electrolyte potential.

Primary Current Distribution (cd) click Initial Values 1.
3 In the phil text field, type (Ecell-Eeq_a-Eeq_c)/2.
MESH 1
The following steps create 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

Boundary Layers.
2 In the Settings window for Boundary Layer Properties, locate the Boundary Selection
section.
3 From the Selection list, choose Anode.
4 Locate the Boundary Layer Properties section. In the Number of boundary layers text
field, type 6.
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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[m].
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
3 From the Calibrate for list, choose Fluid dynamics.
DEFINITIONS
Before solving, create some component couplings to be used when analyzing the results.
Integration 1 (intop1)
1 On the Definitions toolbar, click Component Couplings and choose Integration.
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.
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.
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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
4 Click Add.

Ecell range(1.25,0.05,1.8)
6 In the Model Builder window, click Study 1.

7 In the Settings window for Study, locate the Study Settings section.
8 Clear the Generate default plots check box.
You have now solved the primary current distribution model.
Solution 1 (sol1)
To store this particular primary current distribution solution from the latest computation,
copy and store the solution in order to compare with these results later when you modify
the model.
1 In the Model Builder window, expand the Study 1>Solver Configurations node.
2 Right-click Solution 1 (sol1) and choose Solution>Copy.
Solution 1 - Copy 1 (sol2)

1 In the Model Builder window, under Study 1>Solver Configurations click Solution 1 -
Copy 1 (sol2).
2 In the Settings window for Solution, type Primary current distribution in the Label
text field.
RESULTS
1D Plot Group 1
Now create a polarization plot for the primary current distribution model.
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2 In the Settings window for 1D Plot Group, type Polarization Plot in the Label text
field.
3 Locate the Data section. 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).
9 In the associated text field, type Total current (A).
Global 1
1 Right-click Polarization Plot and choose Global.
2 In the Settings window for Global, locate the Data section.
3 From the Data set list, choose Study 1/Primary current distribution (sol2).
4 Locate the y-Axis Data section. In the table, enter the following settings:

abs(anode_int(cd.nIl)) A
5 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.
2 In the Settings window for 3D Plot Group, type Electrolyte Potential in the Label
text field.
3 Locate the Data section. From the Data set list, choose Study 1/
Primary current distribution (sol2).
4 From the Parameter value (Ecell) list, choose 1.45.
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5 Locate the Plot Settings section. Clear the Plot data set edges check box.
Isosurface 1
1 Right-click Electrolyte Potential and choose Isosurface.
2 On the Electrolyte Potential toolbar, click Plot.
3D Plot Group 3
The following creates a normalized plot of the normal electrolyte current density on the
anode surface.
2 In the Settings window for 3D Plot Group, type Current Density in the Label text field.
3 Locate the Data section. From the Data set list, choose Study 1/
Primary current distribution (sol2).
5 Click to expand the Title section. From the Title type list, choose Manual.
6 In the Title text area, type Dimensionless current density distribution.
Surface 1
1 Right-click Current Density and choose Surface.
Plot the normal current density divided by the average normal current density.
2 In the Settings window for Surface, locate the Expression section.
3 In the Expression text field, type (comp1.cd.nIl)/anode_avg(comp1.cd.nIl).
Selection 1
1 Right-click Results>Current Density>Surface 1 and choose Selection.
2 In the Settings window for Selection, locate the Selection section.
4 On the Current Density toolbar, click Plot.
PRIMARY CURRENT DISTRIBUTION (CD)

Now modify the model to simulate the secondary current distribution.

Primary Current Distribution (cd).
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2 In the Settings window for Primary Current Distribution, locate the
Current Distribution Type section.
3 From the Current distribution type list, choose Secondary.
GLOBAL DEFINITIONS
Parameters
Add the needed parameters for the secondary model.


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

On the Physics toolbar, click Primary Current Distribution (cd) and choose
Now set up the new boundary conditions for the secondary current distribution by adding
the needed kinetics parameters.

Secondary Current Distribution (cd)>Electrode Surface 1 click Electrode Reaction 1.
Butler-Volmer.
5 In the i0 text field, type i0_c.
6 In the αa text field, type be_c.
7 In the αc text field, type 1-be_c.
20 | WIRE ELECTRODE
Butler-Volmer.
5 In the i0 text field, type i0_a.
6 In the αa text field, type be_a.
7 In the αc text field, type 1-be_a.
STUDY 1
On the Home toolbar, click Compute.
RESULTS
Electrolyte Potential
You have now solved the secondary current distribution problem.
STUDY 1
Solution 1 (sol1)
1 In the Model Builder window, under Study 1>Solver Configurations click Solution 1 (sol1).
2 In the Settings window for Solution, type Secondary current distribution in the
Label text field.
RESULTS
Proceed to look at the results by adding the secondary current distribution polarization
plot.
Global 2
1 In the Model Builder window, under Results>Polarization Plot right-click Global 1 and
choose Duplicate.
3 From the Data set list, choose Study 1/Secondary current distribution (sol1).
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Legends
Secondary current distribution
Polarization Plot
1 In the Model Builder window, under Results click Polarization Plot.
Note the 3D plots are now showing the results of the latest computation. (By choosing
different data sets you may compare the primary and secondary current distribution
results.)
1 In the Model Builder window, under Results click Electrolyte Potential.

Current Density
1 In the Model Builder window, under Results click Current Density.
GLOBAL DEFINITIONS
Now modify the problem to model a tertiary current distribution problem by adding mass
transport. Start by adding the parameters.
Parameters
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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
ADD PHYSICS
1 On the Home toolbar, click Add Physics to open the Add Physics window.
3 In the tree, select Chemical Species Transport>Transport of Diluted Species (tds).
ADD PHYSICS
2 In the tree, select Fluid Flow>Single-Phase Flow>Laminar Flow (spf).
4 On the Home toolbar, click Add Physics to close the Add Physics window.
1 In the Settings window for Transport of Diluted Species, locate the Transport Mechanisms
section.
2 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 Input section.
The velocity field will be coupled to Laminar Flow later using the Flow Coupling
multiphysics feature.
4 Locate the Diffusion section. In the Dc text field, type D.
5 Locate the Migration in Electric Field section. In the V text field, type phil.
6 In the zc text field, type -1.
7 In the Model Builder window, click Transport of Diluted Species (tds).
23 | WIRE ELECTRODE
Inflow 1
1 On the Physics toolbar, click Boundaries and choose Inflow.
3 In the Settings window for Inflow, locate the Boundary Selection section.
5 In the Create Selection dialog box, type Inlet in the Selection name text field.
6 Click OK.
7 In the Settings window for Inflow, locate the Concentration section.
8 In the c0,c text field, type c_in.
Outflow 1
1 On the Physics toolbar, click Boundaries and choose Outflow.
3 In the Settings window for Outflow, locate the Boundary Selection section.
5 In the Create Selection dialog box, type Outlet in the Selection name text field.
6 Click OK.
Initial Values 1
3 In the c text field, type c_in.
Electrode Surface 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 Surface Coupling.
2 In the Settings window for Electrode Surface Coupling, locate the Boundary Selection
section.
Reaction Coefficients 1
1 In the Model Builder window, expand the Electrode Surface Coupling 1 node, then click
Reaction Coefficients 1.
2 In the Settings window for Reaction Coefficients, locate the Model Inputs section.
24 | WIRE ELECTRODE
3 From the iloc list, choose Local current density, Electrode Reaction 1 (cd/eebii2/er1).
4 Locate the Stoichiometric Coefficients section. In the νc text field, type 1.

Also modify the current density expression to be concentration dependent.
On the Physics toolbar, click Transport of Diluted Species (tds) and choose
2 In the Settings window for Electrode Reaction, locate the Electrode Kinetics section.
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 (cd) 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 Input section.
4 In the Model Builder window, click 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 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
1 On the Physics toolbar, click Boundaries and choose Outlet.
2 In the Settings window for Outlet, locate the Boundary Selection section.
25 | WIRE ELECTRODE
3 From the Selection list, choose Outlet.
4 Locate the Pressure Conditions section. Select the Normal flow check box.
Wall 2
1 On the Physics toolbar, click Boundaries and choose Wall.
3 In the Settings window for Wall, locate the Boundary Condition section.
4 From the Wall condition list, choose Slip.
MULTIPHYSICS
Finally, set up the Flow Coupling multiphysics feature.
Flow Coupling 1 (fc1)

On the Physics toolbar, click Multiphysics Couplings and choose Global>Flow Coupling.
ROOT
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.
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.
STUDY 2
Step 1: Stationary
2 In the table, clear the Solve for check box for Secondary Current Distribution and
Transport of Diluted Species.
Step 2: Stationary 2
1 On the Study toolbar, click Study Steps and choose Stationary>Stationary.
26 | WIRE ELECTRODE
3 In the table, clear the Solve for check box for Laminar Flow.
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.

Ecell range(1.25,0.05,1.8)
Solution 3 (sol3)
Change to a fully coupled direct solver to decrease solver time.

2 In the Model Builder window, expand the Solution 3 (sol3) node.
3 In the Model Builder window, expand the Study 2>Solver Configurations>
Solution 3 (sol3)>Stationary Solver 2 node.
4 Right-click Study 2>Solver Configurations>Solution 3 (sol3)>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.
7 In the Model Builder window, click Study 2.
8 In the Settings window for Study, locate the Study Settings section.
9 Clear the Generate default plots check box.
You have now solved the tertiary current distribution.
11 In the Label text field, type Tertiary current distribution.
RESULTS
Data Sets
Add the tertiary current distribution to the polarization plot.
Global 3
1 In the Model Builder window, under Results>Polarization Plot right-click Global 2 and
choose Duplicate.
27 | WIRE ELECTRODE
3 From the Data set list, choose Tertiary current distribution/Solution 3 (sol3).
Legends
Tertiary current distribution
3D Plot Group 4
2 In the Settings window for 3D Plot Group, type Velocity in the Label text field.
3 Locate the Data section. From the Data set list, choose Tertiary current distribution/
Solution 3 (sol3).
Slice 1
1 Right-click Velocity and choose Slice.
2 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>
Velocity and pressure>spf.U - Velocity magnitude.
3 Locate the Plane Data section. In the Planes text field, type 7.
4 On the Velocity toolbar, click Plot.
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.
2 In the Settings window for 3D Plot Group, type Concentration in the Label text field.
3 Locate the Data section. From the Data set list, choose Tertiary current distribution/
Solution 3 (sol3).
Arrow Volume 1
1 Right-click Concentration and choose Arrow Volume.
2 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>
Velocity and pressure>u,v,w - Velocity field.
28 | WIRE ELECTRODE
3 Locate the Arrow Positioning section. Find the x grid points subsection. In the Points text
field, type 15.
4 Find the y grid points subsection. In the Points text field, type 15.
5 Find the z grid points subsection. In the Points text field, type 1.
6 Locate the Coloring and Style section. From the Color list, choose Black.
Arrow Volume 2
1 Right-click Results>Concentration>Arrow Volume 1 and choose Duplicate.
2 In the Settings window for Arrow Volume, click to expand the Title section.
3 From the Title type list, choose None.
4 Locate the Arrow Positioning section. Find the y grid points subsection. In the Points text
field, type 1.
5 Find the z grid points subsection. In the Points text field, type 15.
6 Click to expand the Inherit style section. Locate the Inherit Style section. From the Plot
list, choose Arrow Volume 1.
7 On the Concentration toolbar, click Plot.
Concentration
In the Model Builder window, under Results click Concentration.
Multislice 1
1 On the Concentration toolbar, click More Plots and choose Multislice.
2 In the Settings window for Multislice, click Replace Expression in the upper-right corner
of the Expression section. From the menu, choose Component 1>
3 Locate the Multiplane Data section. Find the x-planes subsection. In the Planes text field,
type 0.
Surface 1
1 Right-click Concentration and choose Surface.
2 In the Settings window for Surface, click Replace Expression in the upper-right corner of
the Expression section. From the menu, choose Component 1>
3 Click to expand the Inherit style section. Locate the Inherit Style section. From the Plot
list, choose Multislice 1.
Selection 1
1 Right-click Results>Concentration>Surface 1 and choose Selection.
29 | WIRE ELECTRODE
2 In the Settings window for Selection, locate the Selection section.
4 On the Concentration toolbar, click Plot.
1 In the Model Builder window, under Results click Electrolyte Potential.
Current Density
1 In the Model Builder window, under Results click Current Density.
Appendix — Geometry Modeling Instructions

NEW
In the New window, click Blank Model.
ROOT
On the Home toolbar, click Component and choose Add Component>3D.
GEOMETRY 1
3 From the Length unit list, choose mm.
Block 1 (blk1)
On the Geometry toolbar, click Block.
30 | WIRE ELECTRODE
DEFINITIONS
View 1
1 In the Model Builder window, expand the Component 1 (comp1)>Definitions node, then
click View 1.
2 In the Settings window for View, locate the View section.
3 Select the Wireframe rendering check box.
GEOMETRY 1
Block 1 (blk1)
1 In the Model Builder window, under Component 1 (comp1)>Geometry 1 click
Block 1 (blk1).
2 In the Settings window for Block, locate the Size and Shape section.
3 In the Width text field, type 22.
4 In the Depth text field, type 8.
6 Locate the Position section. In the x text field, type -11.
7 In the y text field, type -4.
8 In the Model Builder window, right-click Geometry 1 and choose Selections>
Cumulative Selections.
9 Right-click Component 1 (comp1)>Geometry 1>Cumulative Selections and choose
Cumulative Selection.
10 In the Settings window for Selection, type Union in the Label text field.
Work Plane 1 (wp1)

1 On the Geometry toolbar, click Work Plane.
2 In the Settings window for Work Plane, locate the Plane Definition section.
3 In the z-coordinate text field, type -1.
Plane Geometry
In the Model Builder window, under Component 1 (comp1)>Geometry 1>
Work Plane 1 (wp1) click Plane Geometry.
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.
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3 In the Side length text field, type 2.
4 Locate the Position section. In the xw text field, type -6.
5 In the yw text field, type -1.
check box.
Fillet 1 (fil1)
1 On the Work Plane toolbar, click Fillet.
2 On the object sq1, select Points 1–4 only.
3 In the Settings window for Fillet, locate the Radius section.
4 In the Radius text field, type 0.5.
check box.
Array 1 (arr1)
1 On the Work Plane toolbar, click Transforms and choose Array.
2 Select the object fil1 only.
3 In the Settings window for Array, locate the Size section.
4 In the xw size text field, type 3.
5 Locate the Displacement section. In the xw text field, type 5.
Extrude 1 (ext1)
1 On the Geometry toolbar, click Extrude.
2 In the Settings window for Extrude, locate the Distances section.
Distances (mm)
6
4 Locate the Selections of Resulting Entities section. From the Contribute to list, choose
Union.
5 Click to expand the Scales section. Click to expand the Displacements section. Click to
expand the Twist angles section. Click to expand the Polygon resolution of edges section.
In the Model Builder window, click Geometry 1.
Work Plane 2 (wp2)

1 On the Geometry toolbar, click Work Plane.
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2 In the Settings window for Work Plane, locate the Plane Definition section.
3 From the Plane list, choose yz-plane.
4 In the x-coordinate text field, type 11.
Plane Geometry
In the Model Builder window, under Component 1 (comp1)>Geometry 1>
Work Plane 2 (wp2) click Plane Geometry.
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.
4 Locate the Position section. From the Base list, choose Center.
check box.
Fillet 1 (fil1)
1 On the Work Plane toolbar, click Fillet.
2 On the object sq1, select Points 1–4 only.
3 In the Settings window for Fillet, locate the Radius section.
4 In the Radius text field, type 0.5.
View 3
In the Model Builder window, expand the Component 1 (comp1)>Geometry 1>
Work Plane 2 (wp2)>View 3 node, then click Geometry 1.
Extrude 2 (ext2)
1 On the Geometry toolbar, click Extrude.
2 In the Settings window for Extrude, locate the Distances section.
Distances (mm)
22

5 Locate the Selections of Resulting Entities section. From the Contribute to list, choose
Union.
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Union 1 (uni1)
3 From the Input objects list, choose Union.
Delete Entities 1 (del1)

1 Right-click Geometry 1 and choose Delete Entities.
2 In the Settings window for Delete Entities, locate the Entities or Objects to Delete section.
5 Click the Select Box button on the Graphics toolbar.
6 Click the Deselect Box button on the Graphics toolbar.
7 Click the Wireframe Rendering button on the Graphics toolbar.
8 On the object uni1, select Domains 1 and 16 only.
Union 2 (uni2)
2 Click the Wireframe Rendering button on the Graphics toolbar.
Delete Entities 1 (del1)

Delete Entities 1 (del1).
2 In the Settings window for Delete Entities, locate the Selections of Resulting Entities
section.
3 Select the Resulting objects selection check box.
Union 2 (uni2)
Union 2 (uni2).
3 From the Input objects list, choose Delete Entities 1.
Difference 1 (dif1)
1 On the Geometry toolbar, click Booleans and Partitions and choose Difference.
2 Select the object blk1 only.
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Union 2 (uni2)
Union 2 (uni2).
2 In the Settings window for Union, locate the Selections of Resulting Entities section.
3 Select the Resulting objects selection check box.
Difference 1 (dif1)
Difference 1 (dif1).
2 In the Settings window for Difference, locate the Difference section.
3 From the Objects to subtract list, choose Union 2.
GEOMETRY 1
Box Selection 1 (boxsel1)

1 On the Geometry toolbar, click Selections and choose Box Selection.
2 In the Settings window for Box Selection, locate the Geometric Entity Level section.
3 From the Level list, choose Boundary.
4 Locate the Box Limits section. In the x minimum text field, type -60.
5 In the x maximum text field, type 60.
6 In the y minimum text field, type -2.
7 In the y maximum text field, type 2.
Explicit Selection 1 (sel1)

1 On the Geometry toolbar, click Selections and choose Explicit Selection.
2 In the Settings window for Explicit Selection, type Cathodes in the Label text field.
3 Click the Zoom Box button on the Graphics toolbar.
4 Locate the Entities to Select section. From the Geometric entity level list, choose
Boundary.
Box Selection 1 (boxsel1)

Box Selection 1 (boxsel1).
2 In the Settings window for Box Selection, type Anode in the Label text field.
3 Locate the Output Entities section. From the Include entity if list, choose
Entity inside box.
35 | WIRE ELECTRODE
Cathodes (sel1)
Cathodes (sel1).
2 In the Settings window for Explicit Selection, locate the Entities to Select section.
3 Find the Entities to select subsection. Select the Active toggle button.
4 Click the Zoom Box button on the Graphics toolbar.
5 On the object dif1, select Boundary 3 only.
7 On the object dif1, select Boundaries 3 and 4 only.
8 Click the Clear Selection button on the Graphics toolbar.
9 On the object dif1, select Boundaries 2 and 5 only.
Hold the Shift key and click on both Anode (boxsel1) and Cathodes (sel1). Right click and
select Move Down.

2 In the Settings window for Explicit Selection, type Inlet in the Label text field.
Boundary.
6 On the object fin, select Boundary 1 only.
Cathodes (sel1)
Right-click Cathodes (sel1) and choose Move Up.

2 In the Settings window for Explicit Selection, type Outlet in the Label text field.
Boundary.
4 On the object fin, select Boundary 52 only.
36 | WIRE ELECTRODE

Electrochemistry Module: Application Library Manual

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Electrochemistry Module

Application Library Manual

• Support Center: www.comsol.com/support

Part number: CM024303

Current Distribution in a Chlor-Alkali Membrane

Inlet brine Anode

Figure 1: Drawing of the unit cell.

A detailed description of the process of chlor-alkali electrolysis is available in Ref. 1.

Figure 2: Model geometry.

E cell = E eq, a – E eq, c + E pol (3)

φ s, c = φ s, a – ( E eq, a – E eq, c + E pol ) (4)

Grounding the electrolyte potential at the anode, φl,a we get:

which is used as a boundary condition for the anode boundary.

In combination with the primary condition above this results in

φ s, c = – ( – E eq, c + E pol ) (6)

Results and Discussion

Figure 3: Electrolyte potential.

Figure 4: Electrolyte current density magnitude.

2. J.S. Newman, Electrochemical Systems, 2nd ed., Prentice Hall, 1991.

3. P. Bosander, P. Byrne, E. Fontes, and O. Parhammar, Current Distribution on a

Application Library path: Electrochemistry_Module/

1 On the Geometry toolbar, click Insert Sequence.

3 On the Geometry toolbar, click Build All.

Property Variable Value Unit Property group

Property Variable Value Unit Property group

Property Variable Value Unit Property group

SECONDARY CURRENT DISTRIBUTION (CD)

Define the potential on the anode by using an Electrolyte Potential node.

1 In the Settings window for Free Triangular, click Build All.

1 On the Home toolbar, click Compute.

Electrolyte Potential (cd)

1 Click the Zoom Extents button on the Graphics toolbar.

Electrolyte Current Density (cd)

Appendix — Geometry Modeling Instructions

Bézier Polygon 1 (b1)

Bézier Polygon 2 (b2)

Cyclic Voltammetry at a Macroelectrode in 1D

Voltammetry is a valuable technique because information about both the electrochemical

In this model, a Parametric Sweep is used to compare voltammetry recorded at different

This is expressed in the Electrode Surface boundary condition.

Figure 2: Cyclic voltammetry recorded at a macroelectrode.

2. A.J. Bard and L.R. Faulkner, Electrochemical Methods, Fundamentals and

Application Library path: Electrochemistry_Module/Tutorials/

1 In the Model Builder window, under Global Definitions click Parameters.

1 In the Model Builder window, under Component 1 (comp1)>Electroanalysis (elan) click

1 On the Physics toolbar, click Boundaries and choose Concentration.

1 On the Physics toolbar, click Boundaries and choose Electrode Surface.

Double Layer Capacitance 1

Parameter name Parameter value list Parameter unit

5 On the Study toolbar, click Compute.

Cyclic Voltammograms (elan)

Diffuse Double Layer

2 | DIFFUSE DOUBLE LAYER

We assume no homogeneous reactions of the ions in solution. Then, conservation of mass

For the potential, the Poisson equation (Gauss’s law) states

3 | DIFFUSE DOUBLE LAYER

If the electrode is inert to electrolysis of the ions at the electrolyte-electrode interface, no

4 | DIFFUSE DOUBLE LAYER

5 | DIFFUSE DOUBLE LAYER

6 | DIFFUSE DOUBLE LAYER

2. D.L. Chapman, Philosophical Magazine, vol. 25, pp. 475-481, 1913.

3. O. Stern, Zeitschrift für Elektrochemie, vol. 30, pp. 508-516, 1924.

4. A.J. Bard and L.R. Faulkner, Electrochemical Methods: Fundamentals and