Electrochemistry Module

User’s Guide
Electrochemistry Module User’s Guide
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Part number: CM024301

C o n t e n t s

Chapter 1: Introduction

About the Electrochemistry Module 14

What Can the Electrochemistry Module Do? . . . . . . . . . . . . 14
The Electrochemistry Module Physics Interface Guide . . . . . . . . . 15
Common Physics Interface and Feature Settings and Nodes . . . . . . 18
Electrochemistry Module Study Availability . . . . . . . . . . . . . 18
Where Do I Access the Documentation and Application Libraries? . . . . 19

Overview of the User’s Guide 24

Chapter 2: Modeling with Electrochemistry

Introduction to Electrochemistry Modeling 28

What is Electrochemistry? . . . . . . . . . . . . . . . . . . . 28
Electrochemical Applications . . . . . . . . . . . . . . . . . . 29
Fundamentals of Electrochemistry Modeling . . . . . . . . . . . . 29
Current Distribution Cases and Choosing the Right Interface to
Model an Electrochemical Cell . . . . . . . . . . . . . . . . 31
Understanding the Different Approximations for Conservation of
Charge in Electrolytes . . . . . . . . . . . . . . . . . . . 32
Modeling Electrochemical Reactions . . . . . . . . . . . . . . . 36
Double Layer Capacitance . . . . . . . . . . . . . . . . . . . 43
Porous Electrodes . . . . . . . . . . . . . . . . . . . . . . 44
Boundary Conditions for Running and Controlling Electrochemical
Cells . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Modeling Cyclic Voltammetry . . . . . . . . . . . . . . . . . . 46
Common Simplifications when Modeling Electrochemical Cells . . . . . 46
Before You Start Building Your Model . . . . . . . . . . . . . . . 48
Meshing Advice . . . . . . . . . . . . . . . . . . . . . . . 50
Solving Electrochemical Models . . . . . . . . . . . . . . . . . 50
Postprocessing Your Solution . . . . . . . . . . . . . . . . . . 55

CONTENTS |3
 Chapter 3: Electrochemistry Interfaces

The Primary and Secondary Current Distribution Interfaces 58

The Primary Current Distribution and Secondary Current Distribution
Interfaces . . . . . . . . . . . . . . . . . . . . . . . . 58
Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . . 61
Initial Values . . . . . . . . . . . . . . . . . . . . . . . . 61
Porous Electrode. . . . . . . . . . . . . . . . . . . . . . . 62
Periodic Condition . . . . . . . . . . . . . . . . . . . . . . 62
Edge Electrode. . . . . . . . . . . . . . . . . . . . . . . . 63
Electrode Line Current Source . . . . . . . . . . . . . . . . . 64
Electrolyte Line Current Source . . . . . . . . . . . . . . . . . 64
Electrode Symmetry Axis Current Source . . . . . . . . . . . . . 64
Electrolyte Symmetry Axis Current Source . . . . . . . . . . . . . 65
Electrode Point Current Source . . . . . . . . . . . . . . . . . 65
Electrolyte Point Current Source. . . . . . . . . . . . . . . . . 65

The Tertiary Current Distribution, Nernst-Planck Interface 66

The Tertiary Current Distribution, Nernst-Planck Interface . . . . . . 66
Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . . 70
Porous Electrode. . . . . . . . . . . . . . . . . . . . . . . 70
Separator. . . . . . . . . . . . . . . . . . . . . . . . . . 71
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . 71
Initial Values . . . . . . . . . . . . . . . . . . . . . . . . 72
Ion Exchange Membrane . . . . . . . . . . . . . . . . . . . . 72
Ion Exchange Membrane Boundary . . . . . . . . . . . . . . . . 73

Shared Physics Features in the Current Distribution Interfaces

75
Domain, Boundary, Pair, Edge, and Point Nodes for the
Electrochemistry Interfaces . . . . . . . . . . . . . . . . . 75
Electrode. . . . . . . . . . . . . . . . . . . . . . . . . . 76
Electrode Current Source . . . . . . . . . . . . . . . . . . . 77
Electrolyte Current Source . . . . . . . . . . . . . . . . . . . 77
Porous Electrode Reaction . . . . . . . . . . . . . . . . . . . 78
Porous Matrix Double Layer Capacitance . . . . . . . . . . . . . 78
Insulation . . . . . . . . . . . . . . . . . . . . . . . . . . 79

4 | CONTENTS
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . . 79
Electrode Surface. . . . . . . . . . . . . . . . . . . . . . . 79
Electrode Reaction . . . . . . . . . . . . . . . . . . . . . . 81
Double Layer Capacitance . . . . . . . . . . . . . . . . . . . 85
Internal Electrode Surface . . . . . . . . . . . . . . . . . . . 85
Electrolyte Potential . . . . . . . . . . . . . . . . . . . . . 86
Electrolyte Current . . . . . . . . . . . . . . . . . . . . . . 86
Electrolyte Current Density. . . . . . . . . . . . . . . . . . . 87
Electrode-Electrolyte Boundary Interface. . . . . . . . . . . . . . 87
Electric Ground . . . . . . . . . . . . . . . . . . . . . . . 88
Electric Potential . . . . . . . . . . . . . . . . . . . . . . . 88
Electrode Current Density . . . . . . . . . . . . . . . . . . . 88
Electrode Current . . . . . . . . . . . . . . . . . . . . . . 89
Electrode Power . . . . . . . . . . . . . . . . . . . . . . . 89
Harmonic Perturbation . . . . . . . . . . . . . . . . . . . . 90
Electrode Potential . . . . . . . . . . . . . . . . . . . . . . 90
External Short . . . . . . . . . . . . . . . . . . . . . . . . 90
Reference Electrode . . . . . . . . . . . . . . . . . . . . . 91
Electric Reference Potential . . . . . . . . . . . . . . . . . . . 91
Circuit Terminal . . . . . . . . . . . . . . . . . . . . . . . 92

The Electrode, Shell Interface 93

Boundary, Edge, Point, and Pair Nodes for the Electrode, Shell
Interface. . . . . . . . . . . . . . . . . . . . . . . . . 94
Electrode. . . . . . . . . . . . . . . . . . . . . . . . . . 95
Initial Values . . . . . . . . . . . . . . . . . . . . . . . . 96
External Current Density . . . . . . . . . . . . . . . . . . . 96
Current Source . . . . . . . . . . . . . . . . . . . . . . . 96
Normal Current Density . . . . . . . . . . . . . . . . . . . . 97
Electric Insulation . . . . . . . . . . . . . . . . . . . . . . 97
Boundary Current Source . . . . . . . . . . . . . . . . . . . 97
Ground . . . . . . . . . . . . . . . . . . . . . . . . . . 97
Electric Potential . . . . . . . . . . . . . . . . . . . . . . . 98

The Electroanalysis Interface 99

Domain, Boundary, and Pair Nodes for the Electroanalysis Interface . . 101
Transport Properties . . . . . . . . . . . . . . . . . . . . 102
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 103

CONTENTS |5
 Electrode Surface in the Electroanalysis Interface. . . . . . . . . . 104
Electrode Reaction . . . . . . . . . . . . . . . . . . . . . 106

Theory for the Current Distribution Interfaces 108

The Nernst-Planck Equations . . . . . . . . . . . . . . . . . 108
Domain Equations for Primary and Secondary Current Distributions . . 109
Electrochemical Reactions and the Difference Between a Primary and
a Secondary Current Distribution . . . . . . . . . . . . . . 110
Domain Equations for Tertiary Current Distributions Using the
Nernst-Planck Equations and Electroneutrality . . . . . . . . . 112
Mass Fluxes and Sources Due to Electrochemical Reactions . . . . . 114
Stochiometric Coefficients for Double Layer Capacitive Charging . . . 115
Film Resistance . . . . . . . . . . . . . . . . . . . . . . 116
Electrode Kinetics Expressions . . . . . . . . . . . . . . . . 116
Theory for Specific Current Distribution Feature Nodes . . . . . . . 118

Theory for Electrochemical Heat Sources 127

Joule Heating Due to Charge Transport . . . . . . . . . . . . . 128
Heating Due to Electrochemical Reactions . . . . . . . . . . . . 128
Heating Due to Heat of Mixing . . . . . . . . . . . . . . . . 129

Theory for the Electrode, Shell Interface 130

Governing Equations . . . . . . . . . . . . . . . . . . . . 130
Coupling to Other Physics Interfaces . . . . . . . . . . . . . . 130

Theory for the Electroanalysis Interface 132

Electroanalytical Methods . . . . . . . . . . . . . . . . . . 132
Supporting Electrolyte . . . . . . . . . . . . . . . . . . . . 133
Domain Equations for the Electroanalysis Interface . . . . . . . . . 134
Electrodes in the Electroanalysis Interface . . . . . . . . . . . . 135
The Electroanalytical Butler–Volmer Equation . . . . . . . . . . . 137
Counter Electrodes and Overall Charge Balance . . . . . . . . . . 138

Electrode Potentials and Reference Electrodes 139

Reference Electrodes . . . . . . . . . . . . . . . . . . . . 139
Boundary Conditions Using Reference Electrode Potentials. . . . . . 140
Nodes for Handling Electrode Potentials and Reference Electrodes. . . 140

6 | CONTENTS
 Solving Electrochemical Models 142
General Current Distribution Problems . . . . . . . . . . . . . 142
Electrochemistry Coupled to Mass Transport . . . . . . . . . . . 143
Setting up a Study Sequence for Multiphysics Problems . . . . . . . 143
Time-dependent Problems with Load Steps . . . . . . . . . . . . 144
Solver Settings . . . . . . . . . . . . . . . . . . . . . . . 145

Chapter 4: Chemical Species Transport Interfaces

The Transport of Diluted Species Interface 148

The Transport of Diluted Species in Porous Media Interface . . . . . 152
Domain, Boundary, and Pair Nodes for the Transport of Diluted
Species Interface. . . . . . . . . . . . . . . . . . . . . 153
Transport Properties . . . . . . . . . . . . . . . . . . . . 155
Turbulent Mixing . . . . . . . . . . . . . . . . . . . . . . 157
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 158
Mass-Based Concentrations . . . . . . . . . . . . . . . . . . 158
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 158
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 160
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 160
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 161
Concentration . . . . . . . . . . . . . . . . . . . . . . . 161
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 162
Flux Discontinuity . . . . . . . . . . . . . . . . . . . . . 162
Partition Condition . . . . . . . . . . . . . . . . . . . . . 163
Periodic Condition . . . . . . . . . . . . . . . . . . . . . 164
Line Mass Source . . . . . . . . . . . . . . . . . . . . . . 164
Point Mass Source . . . . . . . . . . . . . . . . . . . . . 165
Open Boundary . . . . . . . . . . . . . . . . . . . . . . 166
Thin Diffusion Barrier . . . . . . . . . . . . . . . . . . . . 166
Thin Impermeable Barrier . . . . . . . . . . . . . . . . . . 166
Equilibrium Reaction . . . . . . . . . . . . . . . . . . . . 167
Surface Reactions . . . . . . . . . . . . . . . . . . . . . 168
Surface Equilibrium Reaction . . . . . . . . . . . . . . . . . 168
Fast Irreversible Surface Reaction . . . . . . . . . . . . . . . 169

CONTENTS |7
 Porous Electrode Coupling . . . . . . . . . . . . . . . . . . 169
Reaction Coefficients . . . . . . . . . . . . . . . . . . . . 170
Electrode Surface Coupling . . . . . . . . . . . . . . . . . . 170
Porous Media Transport Properties. . . . . . . . . . . . . . . 171
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . 173
Partially Saturated Porous Media . . . . . . . . . . . . . . . . 174
Volatilization . . . . . . . . . . . . . . . . . . . . . . . 176
Reactive Pellet Bed . . . . . . . . . . . . . . . . . . . . . 177
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 180
Species Source. . . . . . . . . . . . . . . . . . . . . . . 181
Hygroscopic Swelling . . . . . . . . . . . . . . . . . . . . 182
Fracture . . . . . . . . . . . . . . . . . . . . . . . . . 183

The Chemistry Interface 184

Feature Nodes Available for the Chemistry Interface . . . . . . . . 187
Reaction . . . . . . . . . . . . . . . . . . . . . . . . . 187
Species . . . . . . . . . . . . . . . . . . . . . . . . . 191
Reversible Reaction Group . . . . . . . . . . . . . . . . . . 193
Equilibrium Reaction Group. . . . . . . . . . . . . . . . . . 194
Species Group . . . . . . . . . . . . . . . . . . . . . . . 196
Reaction Thermodynamics . . . . . . . . . . . . . . . . . . 196
Species Activity . . . . . . . . . . . . . . . . . . . . . . 196
Species Thermodynamics. . . . . . . . . . . . . . . . . . . 196

The Nernst-Planck-Poisson Equations Interface 198

The Electrophoretic Transport Interface 200

Common Settings for the Species nodes in the Electrophoretic
Transport Interface . . . . . . . . . . . . . . . . . . . 204
Diffusion and Migration Settings . . . . . . . . . . . . . . . . 205
Domain, Boundary, and Pair Nodes for the Electrophoretic Transport
Interface. . . . . . . . . . . . . . . . . . . . . . . . 206
Solvent . . . . . . . . . . . . . . . . . . . . . . . . . 207
Porous Matrix Properties . . . . . . . . . . . . . . . . . . 207
Fully Dissociated Species . . . . . . . . . . . . . . . . . . . 208
Uncharged Species . . . . . . . . . . . . . . . . . . . . . 208
Weak Acid . . . . . . . . . . . . . . . . . . . . . . . . 208
Weak Base . . . . . . . . . . . . . . . . . . . . . . . . 208

8 | CONTENTS
Ampholyte . . . . . . . . . . . . . . . . . . . . . . . . 209
Protein . . . . . . . . . . . . . . . . . . . . . . . . . 209
Current Source . . . . . . . . . . . . . . . . . . . . . . 209
Initial Potential. . . . . . . . . . . . . . . . . . . . . . . 209
Current . . . . . . . . . . . . . . . . . . . . . . . . . 210
Current Density . . . . . . . . . . . . . . . . . . . . . . 210
Insulation . . . . . . . . . . . . . . . . . . . . . . . . . 210
Potential . . . . . . . . . . . . . . . . . . . . . . . . . 210
Species Source. . . . . . . . . . . . . . . . . . . . . . . 211
Initial Concentration . . . . . . . . . . . . . . . . . . . . 211
Concentration . . . . . . . . . . . . . . . . . . . . . . . 211
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 211
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 212
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 213

The Surface Reactions Interface 214

Boundary, Edge, Point, and Pair Nodes for the Surface Reactions
Interface. . . . . . . . . . . . . . . . . . . . . . . . 215
Surface Properties . . . . . . . . . . . . . . . . . . . . . 216
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 217
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 217
Surface Concentration . . . . . . . . . . . . . . . . . . . . 218

Theory for the Transport of Diluted Species Interface 219

Mass Balance Equation . . . . . . . . . . . . . . . . . . . . 220
Equilibrium Reaction Theory . . . . . . . . . . . . . . . . . 221
Convective Term Formulation. . . . . . . . . . . . . . . . . 223
Solving a Diffusion Equation Only . . . . . . . . . . . . . . . 223
Mass Sources for Species Transport . . . . . . . . . . . . . . 224
Adding Transport Through Migration . . . . . . . . . . . . . . 225
Supporting Electrolytes . . . . . . . . . . . . . . . . . . . 227
Crosswind Diffusion . . . . . . . . . . . . . . . . . . . . 228
Danckwerts Inflow Boundary Condition . . . . . . . . . . . . . 229
Transport of Diluted Species in Porous Media . . . . . . . . . . . 229
Convection . . . . . . . . . . . . . . . . . . . . . . . . 231
Convective Term Formulation. . . . . . . . . . . . . . . . . 232
Diffusion . . . . . . . . . . . . . . . . . . . . . . . . . 233

CONTENTS |9
 Dispersion . . . . . . . . . . . . . . . . . . . . . . . . 234
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . 235
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 236
Theory for the Reactive Pellet Bed . . . . . . . . . . . . . . . 237
References . . . . . . . . . . . . . . . . . . . . . . . . 242

Theory for the Electrophoretic Transport Interface 243

Theory for the Surface Reactions Interface 249

Governing Equations for the Surface Concentrations . . . . . . . . 249
Governing Equations for the Bulk Concentrations . . . . . . . . . 250
ODE-Formulations for Surface Concentrations . . . . . . . . . . 252
Surface Reaction Equations on Deforming Geometries . . . . . . . 253
Reference for the Surface Reactions Interface . . . . . . . . . . . 254

Theory for the Coupling of Mass Transport to

Electrochemical Reactions 255
Molar Sources and Sinks . . . . . . . . . . . . . . . . . . . 255
Mass Sources and Sinks . . . . . . . . . . . . . . . . . . . 256

Chapter 5: Fluid Flow Interfaces

The Darcy’s Law Interface 258

Domain, Boundary, Edge, Point, and Pair Nodes for the Darcy’s
Law Interface . . . . . . . . . . . . . . . . . . . . . . 259
Fluid and Matrix Properties . . . . . . . . . . . . . . . . . . 261
Mass Source . . . . . . . . . . . . . . . . . . . . . . . 262
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 262
Porous Electrode Coupling . . . . . . . . . . . . . . . . . . 262
Electrode Surface Coupling . . . . . . . . . . . . . . . . . . 263
Pressure . . . . . . . . . . . . . . . . . . . . . . . . . 263
Mass Flux. . . . . . . . . . . . . . . . . . . . . . . . . 264
Inlet . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 265
No Flow . . . . . . . . . . . . . . . . . . . . . . . . . 265
Flux Discontinuity . . . . . . . . . . . . . . . . . . . . . 265

10 | C O N T E N T S
Outlet . . . . . . . . . . . . . . . . . . . . . . . . . . 266
Cross Section . . . . . . . . . . . . . . . . . . . . . . . 266
Thickness. . . . . . . . . . . . . . . . . . . . . . . . . 266

The Free and Porous Media Flow Interface 268

Domain, Boundary, Point, and Pair Nodes for the Free and Porous
Media Flow Interface . . . . . . . . . . . . . . . . . . . 269
Fluid Properties . . . . . . . . . . . . . . . . . . . . . . 270
Fluid and Matrix Properties . . . . . . . . . . . . . . . . . . 271
Volume Force . . . . . . . . . . . . . . . . . . . . . . . 272
Forchheimer Drag . . . . . . . . . . . . . . . . . . . . . 272
Porous Electrode Coupling . . . . . . . . . . . . . . . . . . 272
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 273
Electrode-Electrolyte Interface Coupling . . . . . . . . . . . . . 273
Wall . . . . . . . . . . . . . . . . . . . . . . . . . . 274

The Brinkman Equations Interface 275

Domain, Boundary, Point, and Pair Nodes for the Brinkman
Equations Interface . . . . . . . . . . . . . . . . . . . . 277
Fluid and Matrix Properties . . . . . . . . . . . . . . . . . . 278
Forchheimer Drag . . . . . . . . . . . . . . . . . . . . . 279
Mass Source . . . . . . . . . . . . . . . . . . . . . . . 279
Volume Force . . . . . . . . . . . . . . . . . . . . . . . 280
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 280
Fluid Properties . . . . . . . . . . . . . . . . . . . . . . 280

Theory for the Darcy’s Law Interface 282

Darcy’s Law — Equation Formulation . . . . . . . . . . . . . . 282

Theory for the Free and Porous Media Flow Interface 284
Reference for the Free and Porous Media Flow Interface. . . . . . . 284

Theory for the Brinkman Equations Interface 285

About the Brinkman Equations . . . . . . . . . . . . . . . . 285
Brinkman Equations Theory. . . . . . . . . . . . . . . . . . 285
References for the Brinkman Equations Interface. . . . . . . . . . 287

Theory for the Coupling of Fluid Flow to Electrochemical

CONTENTS | 11
 Reactions 288
Momentum Sources and Sinks . . . . . . . . . . . . . . . . . 288

Chapter 6: Heat Transfer Interfaces

Coupling of Heat Transfer to Electrochemical Reactions 290

Joule Heating Due to Charge Transport . . . . . . . . . . . . . 291
Heating Due to Electrochemical Reactions . . . . . . . . . . . . 291

Chapter 7: Multiphysics Coupling Nodes

Electrochemical Heating . . . . . . . . . . . . . . . . . . . 296
Flow Coupling . . . . . . . . . . . . . . . . . . . . . . . 296
Potential Coupling . . . . . . . . . . . . . . . . . . . . . 297
Space Charge Density Coupling . . . . . . . . . . . . . . . . 297
Temperature Coupling . . . . . . . . . . . . . . . . . . . 297

Chapter 8: Glossary

Glossary of Terms 300

12 | C O N T E N T S
 1

Introduction

This guide describes the Electrochemistry Module, an optional add-on package

for COMSOL Multiphysics®.

This chapter introduces you to the capabilities of this module including an

introduction to the modeling stages and some realistic and illustrative models. A
summary of the physics interfaces and where you can find documentation and
model examples is also included. The last section is a brief overview with links to
each chapter in this guide.

In this chapter:

• About the Electrochemistry Module

• Overview of the User’s Guide

13
 About the Electrochemistry Module
These topics are included in this section:

• What Can the Electrochemistry Module Do?

• The Electrochemistry Module Physics Interface Guide
• Common Physics Interface and Feature Settings and Nodes
• Electrochemistry Module Study Availability
• Where Do I Access the Documentation and Application Libraries?

The Physics Interfaces and Building a COMSOL Multiphysics Model in

the COMSOL Multiphysics Reference Manual

What Can the Electrochemistry Module Do?

The Electrochemistry Module extends the COMSOL Multiphysics environment with
customized physics interfaces for modeling of electrochemical cells, with tools for
building detailed models of the configuration of electrodes and electrolyte. The physics
interfaces include descriptions of the electrochemical reactions and the transport
properties that influence the behavior of various types of electrochemical cells. With
this module, you have the perfect tools to investigate the influence of using different
materials, geometric configurations, and operating conditions on the behavior of a cell.

The targeted applications for this module are the following:

• Electroanalysis
• Rotating disc electrodes
• Voltammetry
• Chronoamperometry
• Electrochemical impedance spectroscopy
• Electrochemical sensors
• Electrolysis
• Electrodialysis
• Biosensors
• Electrochemical nanotechnology

14 | CHAPTER 1: INTRODUCTION
The physics interfaces include chemical species transport, charge balances, heat
transfer, and fluid flow. You can use the module to model electrochemical and
electroanalytical procedures in electrochemical cells at different operating conditions
for different electrode configurations, structures and dimensions; and different
electrode and electrolyte materials and chemistry.

The module adds the electrochemistry interfaces, which contains the Electroanalysis
interface and the Primary Current Distribution, Secondary Current Distribution, and
Tertiary Current Distribution, Nernst-Planck interfaces. The current distribution
interfaces are available for solid nonporous electrodes and for porous electrodes.
General tertiary current distribution models can also be set up using the Chemical
Species Transport interfaces.

The tailored physics interfaces mentioned above are also complemented with extended
functionality in other physics interfaces for chemical species transport, heat transfer,
and fluid flow.

The physics interfaces for chemical species transport of neutral species are extended by
adding functionality that directly couples to electrochemical reactions defined in the
physics interfaces for electrochemical cells.

Heat Transfer Interfaces includes heat sources that describe ohmic losses in the
electrodes and electrolyte and heat sources due to electrochemical reactions in
electrochemical cells.

The fluid flow capabilities are extended for laminar flow, where the chemical species
transport and the energy balances influence the properties of the flow.

The Electrochemistry Module Physics Interface Guide

The Electrochemistry Module extends the functionality of the physics interfaces for
the base package of COMSOL Multiphysics. The details of the physics interfaces and
study types for the Electrochemistry Module are listed in the table. The functionality

ABOUT THE ELECTROCHEMISTRY MODULE | 15

 of the COMSOL Multiphysics base package is listed in the COMSOL Multiphysics
Reference Manual.

In the COMSOL Multiphysics Reference Manual:

• Studies and Solvers

• The Physics Interfaces
• For a list of all the core physics interfaces included with a COMSOL
Multiphysics license, see Physics Interface Guide.

PHYSICS INTERFACE ICON TAG SPACE AVAILABLE STUDY TYPE

DIMENSION

Chemical Species Transport

Surface Reactions sr all dimensions stationary (3D, 2D, and 2D

axisymmetric models only);
time dependent
Transport of Diluted tds all dimensions stationary; time dependent
Species
Transport of Diluted tds all dimensions stationary; time dependent
Species in Porous Media
Electrophoretic Transport el all dimensions stationary; stationary with
initialization; time
dependent; time dependent
with initialization
Nernst-Planck-Poisson tds+es all dimensions stationary; time dependent;
Equations stationary source sweep;
small-signal analysis,
frequency domain
Reacting Flow

Laminar Flow, Diluted — 3D, 2D, 2D stationary; time dependent

Species axisymmetric

16 | CHAPTER 1: INTRODUCTION
PHYSICS INTERFACE ICON TAG SPACE AVAILABLE STUDY TYPE
DIMENSION

Electrochemistry

Primary Current cd all dimensions stationary; stationary with

Distribution initialization; time
dependent; time dependent
with initialization; AC
Secondary Current
impedance, initial values;
Distribution
AC impedance, stationary;
AC impedance, time
dependent
Tertiary Current tcd all dimensions stationary; stationary with
Distribution, initialization; time
Nernst-Planck dependent; time dependent
(Electroneutrality, with initialization; AC
Water-Based with impedance, initial values;
Electroneutrality, AC impedance, stationary;
Supporting Electrolyte) AC impedance, time
dependent
Electroanalysis elan all dimensions stationary; time dependent;
AC impedance, initial
values; AC impedance,
stationary; AC impedance,
time dependent; cyclic
voltammetry
Electrode, Shell els 3D, 2D, 2D stationary; time dependent
axisymmetric
Fluid Flow

Porous Media and Subsurface Flow

Brinkman Equations br 3D, 2D, 2D stationary; time dependent

axisymmetric
Darcy’s Law dl all dimensions stationary; time dependent

Free and Porous Media fp 3D, 2D, 2D stationary; time dependent

Flow axisymmetric

ABOUT THE ELECTROCHEMISTRY MODULE | 17

 PHYSICS INTERFACE ICON TAG SPACE AVAILABLE STUDY TYPE
DIMENSION

Heat Transfer

Heat Transfer in Porous ht all dimensions stationary; time dependent

Media

Common Physics Interface and Feature Settings and Nodes

There are several common settings and sections available for the physics interfaces and
feature nodes. Some of these sections also have similar settings or are implemented in
the same way no matter the physics interface or feature being used. There are also some
physics feature nodes that display in COMSOL Multiphysics.

In each module’s documentation, only unique or extra information is included;

standard information and procedures are centralized in the COMSOL Multiphysics
Reference Manual.

In the COMSOL Multiphysics Reference Manual see Table 2-3 for

links to common sections and Table 2-4 to common feature nodes.
You can also search for information: press F1 to open the Help
window or Ctrl+F1 to open the Documentation window.

Electrochemistry Module Study Availability

Studies and Solvers in the COMSOL Multiphysics Reference Manual

18 | CHAPTER 1: INTRODUCTION
TABLE 1-1: MODULE DEPENDENT PHYSICS INTERFACES AND STUDY AVAILABILITY
*
PHYSICS INTERFACE NAME PRESET STUDIES

AC IMPEDANCE TIME
TIME DEPENDENT

AC IMPEDANCE
STATIONARY

STATIONARY

DEPENDENT
Surface Reactions sr √ √
Transport of Diluted Species tds √ √
Transport of Diluted Species in tds √ √
Porous Media
Primary Current Distribution siec √
Secondary Current Distribution siec √ √ √ √
Tertiary Current Distribution, tcdee √ √ √ √
Nernst-Planck
Electroanalysis elan √ √ √ √
Laminar Flow spf √ √
Brinkman Equations br √ √
Darcy’s Law dl √ √
Free and Porous Media Flow fp √ √
Heat Transfer in Porous Media ht √ √
*Custom studies are also available

Where Do I Access the Documentation and Application Libraries?

A number of internet resources have more information about COMSOL, including
licensing and technical information. The electronic documentation, topic-based (or

ABOUT THE ELECTROCHEMISTRY MODULE | 19

 context-based) help, and the application libraries are all accessed through the
COMSOL Desktop.

If you are reading the documentation as a PDF file on your computer,

the blue links do not work to open an application or content
referenced in a different guide. However, if you are using the Help
system in COMSOL Multiphysics, these links work to open other
modules, application examples, and documentation sets.

THE DOCUMENTATION AND ONLINE HELP

The COMSOL Multiphysics Reference Manual describes the core physics interfaces
and functionality included with the COMSOL Multiphysics license. This book also has
instructions about how to use COMSOL Multiphysics and how to access the
electronic Documentation and Help content.

Opening Topic-Based Help

The Help window is useful as it is connected to the features in the COMSOL Desktop.
To learn more about a node in the Model Builder, or a window on the Desktop, click
to highlight a node or window, then press F1 to open the Help window, which then
displays information about that feature (or click a node in the Model Builder followed
by the Help button ( ). This is called topic-based (or context) help.

To open the Help window:

• In the Model Builder, Application Builder, or Physics Builder click a node or

window and then press F1.
• On any toolbar (for example, Home, Definitions, or Geometry), hover the
mouse over a button (for example, Add Physics or Build All) and then
press F1.
• From the File menu, click Help ( ).
• In the upper-right corner of the COMSOL Desktop, click the Help ( )
button.

20 | CHAPTER 1: INTRODUCTION
 To open the Help window:

• In the Model Builder or Physics Builder click a node or window and then
press F1.
• On the main toolbar, click the Help ( ) button.
• From the main menu, select Help>Help.

Opening the Documentation Window

To open the Documentation window:

• Press Ctrl+F1.
• From the File menu select Help>Documentation ( ).

To open the Documentation window:

• Press Ctrl+F1.
• On the main toolbar, click the Documentation ( ) button.
• From the main menu, select Help>Documentation.

THE APPLICATION LIBRARIES WINDOW

Each model or application includes documentation with the theoretical background
and step-by-step instructions to create a model or app. The models and applications
are available in COMSOL Multiphysics as MPH files that you can open for further
investigation. You can use the step-by-step instructions and the actual models as
templates for your own modeling. In most models, SI units are used to describe the
relevant properties, parameters, and dimensions, but other unit systems are available.

Once the Application Libraries window is opened, you can search by name or browse
under a module folder name. Click to view a summary of the model or application and
its properties, including options to open it or its associated PDF document.

The Application Libraries Window in the COMSOL Multiphysics

Reference Manual.

ABOUT THE ELECTROCHEMISTRY MODULE | 21

 Opening the Application Libraries Window
To open the Application Libraries window ( ):

• From the Home toolbar, Windows menu, click ( ) Applications

Libraries.
• From the File menu select Application Libraries.

To include the latest versions of model examples, from the File>Help

menu, select ( ) Update COMSOL Application Library.

Select Application Libraries from the main File> or Windows> menus.

To include the latest versions of model examples, from the Help menu
select ( ) Update COMSOL Application Library.

CONTACTING COMSOL BY EMAIL

For general product information, contact COMSOL at [email protected].

COMSOL ACCESS AND TECHNICAL SUPPORT

To receive technical support from COMSOL for the COMSOL products, please
contact your local COMSOL representative or send your questions to
[email protected]. An automatic notification and a case number are sent to you by
email. You can also access technical support, software updates, license information, and
other resources by registering for a COMSOL Access account.

COMSOL ONLINE RESOURCES

COMSOL website www.comsol.com

Contact COMSOL www.comsol.com/contact
COMSOL Access www.comsol.com/access
Support Center www.comsol.com/support
Product Download www.comsol.com/product-download
Product Updates www.comsol.com/support/updates
COMSOL Blog www.comsol.com/blogs
Discussion Forum www.comsol.com/community
Events www.comsol.com/events

22 | CHAPTER 1: INTRODUCTION
COMSOL Video Gallery www.comsol.com/video
Support Knowledge Base www.comsol.com/support/knowledgebase

ABOUT THE ELECTROCHEMISTRY MODULE | 23

 Overview of the User’s Guide
The Electrochemistry Module User’s Guide gets you started with modeling using
COMSOL Multiphysics. The information in this guide is specific to this module.
Instructions how to use COMSOL in general are included with the COMSOL
Multiphysics Reference Manual.

As detailed in the section Where Do I Access the Documentation and

Application Libraries? this information can also be searched from the
COMSOL Multiphysics software Help menu.

TABLE OF CONTENTS, GLOSSARY, AND INDEX

To help you navigate through this guide, see the Contents, Glossary of Terms, and
Index.

MODELING WITH ELECTROCHEMISTRY

The Modeling with Electrochemistry chapter discusses a variety of topics, including
Fundamentals of Electrochemistry Modeling, Modeling Electrochemical Reactions,
Modeling Cyclic Voltammetry, and Postprocessing Your Solution.

ELECTROCHEMISTRY INTERFACES
Electrochemistry Interfaces chapter describes the Primary Current Distribution,
Secondary Current Distribution, Tertiary Current Distribution, Nernst-Planck,
Current Distribution on Edges, BEM, Electrode, Shell, and Electroanalysis interfaces.
The chapter also includes the underlying theory.

CHEMICAL SPECIES TRANSPORT INTERFACES

Chemical Species Transport Interfaces chapter describes the Transport in Diluted
Species, Transport of Diluted Species in Porous Media, and Surface Reactions
interfaces. It also includes sections about the underlying theory for each physics
interface.

FLUID FLOW INTERFACES

Fluid Flow Interfaces chapter describes the Darcy’s Law, Free and Porous Media Flow,
and the Brinkman Equations interfaces, including the underlying theory for each.

24 | CHAPTER 1: INTRODUCTION
HEAT TRANSFER INTERFACES
Heat Transfer Interfaces chapter describes how to couple electrochemical heat sources
to heat transfer.

THE MULTIPHYSICS COUPLING NODES

The Multiphysics Coupling Nodes chapter describes the coupling nodes available
under the Multiphysics node for coupling various electrochemical interfaces using
flow, potential, and temperature couplings, for example.

OVERVIEW OF THE USER’S GUIDE | 25

26 | CHAPTER 1: INTRODUCTION
 2

Modeling with Electrochemistry

In this chapter you are given an Introduction to Electrochemistry Modeling.

27
 Introduction to Electrochemistry
Modeling
In this section:

• What is Electrochemistry?
• Electrochemical Applications
• Fundamentals of Electrochemistry Modeling
• Current Distribution Cases and Choosing the Right Interface to Model an
Electrochemical Cell
• Understanding the Different Approximations for Conservation of Charge in
Electrolytes
• Modeling Electrochemical Reactions
• Double Layer Capacitance
• Porous Electrodes
• Boundary Conditions for Running and Controlling Electrochemical Cells
• Modeling Cyclic Voltammetry
• Common Simplifications when Modeling Electrochemical Cells
• Before You Start Building Your Model
• Meshing Advice
• Solving Electrochemical Models
• Postprocessing Your Solution

What is Electrochemistry?
An electrochemical process is one that either converts electrical energy to chemical
energy or converts chemical energy to electrical energy.

In electrochemical reactions, chemicals react by gaining or losing electrons. Chemicals

can exchange these electrons with an electrical conductor or circuit. The chemical
potential — or thermodynamic driving force — for a chemical reaction is thus
converted into an electrical potential or voltage, which can be exploited to do useful
work when electrical current is drawn.

28 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

Electrochemical Applications
Electrochemical systems may be classified in different ways.

One approach is to contrast those electrochemical systems involving desirable reactions

from those involving undesirable reactions. Synthetic electrolysis is an example of a
desirable reaction because the chemical process is promoted to generate a desired
product. Or, in designing a battery, for example, we might want to set up conditions
to promote an electrochemical reaction in order to extract useful energy.

Corrosion is an example of undesirable electrochemistry because in this case

spontaneous electrochemical reactions destroy structural materials and so harm the
integrity of a system: we aim to minimize the rate of these reactions.

Electrochemical systems can also be classified into systems that output energy or
systems that consume energy. Batteries and fuel cells are energy extraction devices —
an electrochemical reaction is used to convert the energy in chemical system into a
voltage. Such cells are also called galvanic cells. By contrast, in electrolysis, the system
consumes energy to promote an electrochemical reaction for synthesis. Similar
electrochemical systems needing energy input include manufacturing processes such as
electroplating. Electrochemical reactions may also be driven for electroanalysis, to
quantify or otherwise explore the chemical constituents or reactivity of a system.

The different electrochemical modules in COMSOL Multiphysics are designed to

offer tailored physics interfaces provision for each of these electrochemical situations.
The underlying physical description provided by the general physics interfaces
described below is common to all the modules — the differences between the modules
lies in the particular expected system inputs and outputs and the intended behavior of
the system.

Fundamentals of Electrochemistry Modeling

Electrochemical systems consist of electrically conducting media. These may be
classified as electrodes or electrolyte. An electrode carries current by transport of
electrons; normally the electrode is a conventional electrical conductor such as a metal.
The electrolyte carries current by transport of charged chemical species (ions).
Electrolytes are often salt solutions in water but may include salt solutions in other
liquid solvents, as well as solids, such as concrete, which can conduct by transport of
oxide ions. The electrical conductivity of an electrode is normally several orders of
magnitude larger than the electrical conductivity of an electrolyte.

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 29

 THE ELECTRODE-ELECTROLYTE INTERFACE
At the electrode-electrolyte interface, conventional electrical current in the electrode
is converted into ionic current in the electrolyte. According to the overall conservation
of charge, these currents must balance here. The conversion between the two types of
current may arise due to electrochemical reaction (electrolysis) or capacitive charging.

Electrolysis occurs when a chemical species in the electrolyte exchanges one or more
electrons with the electrode. Capacitive charging occurs when the potential of an
electrode is changing, so that ions in the electrolyte are either attracted or repelled
from the surface, drawing a current.

Batteries and fuel cells can also involve porous electrodes, in which an electrode
material has a micro- or nanostructure that is permeable to electrolyte. The advantage
of such a material is the great increase in the area of the electrode-electrolyte interface.

Note that all current must move in circuits. An isolated electrode-electrolyte interface
cannot draw a net current, but a system with two such interfaces can. An
electrochemical system with two or more electrodes in contact with electrolyte is called
an electrochemical cell.

In an electrochemical cell with two electrodes, these electrodes are identified as an

anode, at which the electrochemical reaction transfers electrons from electrolyte to
electrode, and a cathode, at which electrons are transfered from the electrode to the
electrolyte. Note that it is the direction of the current that will determine if an
electrode reaction is anodic or cathodic. For a battery, for instance, the location of the
anode and cathode will change depending on whether the battery is charged or
discharged. (The general habit in the battery community to always denounce the
positive electrode as the “cathode” is hence strictly only correct during battery
discharge.)

Conventional electric current is the flow of positive charge, which is then from anode
to cathode through the electrolyte. A closed circuit, conserving overall system charge,
is formed by the flow of electric current in the electrode domains (and any electrical
circuitry) from cathode to anode, and by the transport of ions through the electrolyte
domains from anode to cathode.

OUTPUTS OF INTEREST FROM A MODEL

The experimentally measurable features of an electrochemical system are the external
(lumped) current and voltage acting between the two electrodes. It is, in general,
impossible to measure local current densities or potentials at different points on the

30 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

surface of a conducting electrode, or at arbitrary points within an electrochemical
system.

The advantage of physical modeling is the ability to investigate the full

space-dependent behavior of the system under a wide range of circumstances to
identify the reasons for the observed current-voltage relationship, and so to identify
the appropriate physical conditions to optimize current and voltage as required.

The overall current-voltage curve of an electrochemical cell is also known as a

polarization curve or, in an analytical context, a voltammogram. These curves are not
unique but rather depend on the means by which the current or voltage is altered, since
these lumped parameters are related to multiple physical effects with different length
and time scales. Hysteresis in practical polarization curves is not uncommon.

Polarization curves are frequently nonlinear. The combination of nonlinearity and

hysteresis means that electrochemical cells do not necessarily resemble “ideal”
electrical components (such as a circuit of resistors and capacitors) in the sense of
giving a predictable and linear current-voltage response.

• Potential Variables
• Current Variables and Calculating the Total Cell Current

Current Distribution Cases and Choosing the Right Interface to

Model an Electrochemical Cell
COMSOL Multiphysics has many built-in physics interfaces aimed at specific
applications. In many generic cases, however, the modeler has to make some basic
assumptions about his system before starting to build his model.

Under the assumption of a linear relation of current density to electric field, Ohm’s law
is obeyed for the electrolyte current. This is the assumption of primary current
distribution, where one also assumes infinitely fast electrodes kinetics, resulting in
negligible potential drops over the electrode-electrolyte interfaces. If the electrode
reaction kinetics proceed at a finite rate, then the system has a secondary current
distribution. In the cases of more advanced nonlinear charge conservation equations
being required and concentration-dependent electrode polarization, the system is
described as obeying tertiary current distribution.

In some applications, especially within the field of electroanalysis, the potential

gradients in the electrolyte are so small that the spatial distribution of current in the

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 31

 electrolyte is not solved for. Such models are instead centered around the interplay of
electrode kinetics and transport (by diffusion) of the reacting species in the vicinity of
the electrode.

A rule-of-thumb flow chart for selecting a proper current distribution interface for a
model is shown below. The recommendations here are indicative and the modeler may
sometimes wish to deviate from the suggested route; in particular, simpler descriptions
are recommended at an earlier stage of model development. In the following sections
we explain some of the theory behind this flow chart with regards to the description
of the electrolyte charge transport and electrode reactions.

Understanding the Different Approximations for Conservation of

Charge in Electrolytes
Deciding how to model the charge transport in the electrolyte is usually the starting
point when setting up an electrochemical model since this will determine what physics

32 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

interface you will use when starting to build your model. Different theoretical
descriptions of the electrolyte current density are included in COMSOL Multiphysics.
They are applicable in different circumstances as discussed in this section.

The electric displacement field in a medium is related to the local charge density
according to Gauss’s law, one of Maxwell’s equations:

∇ ⋅ D = ρv

In electrolytes, we can normally assume that the electrical permittivity is constant and
equal to a bulk value:

D = ε 0 ε s E = – ε 0 ε s ∇V

Hence

2 ρv
∇ V + ---------- = 0
ε0 εs

In an electrolyte with ionic charge carriers, the charge density can be written as:

ρv = F  zi ci
i

Hence

F
ε0 εs 
2
∇ V + ---------- zi ci = 0
i

This is the Poisson equation relating the electrolyte potential to the distribution of
charge carriers within the electrolyte. In its derivation we assumed that the only charge
carriers are ions, and that the solvated ions and electric field do not alter the
permittivity of the medium.

The mass transport of the charge carriers in aqueous systems is normally given by the
Nernst-Planck equations. These equations neglect ion-ion interactions, and so they
are only exact for infinitely dilute solutions:

N i = – D i ∇c i – z i u m, i Fc i ∇φ l + c i u

Note that concentrated electrolyte systems, such as those in many batteries, use an
extended concentrated species flux definition, based on the Maxwell-Stefan set of

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 33

 equations. This will result in a different set of equations to solve for, but the general
principles and conclusion in this section will be the same.

Substituting the Nernst-Einstein relation for the electrical mobility of an ion we get:

ziF
N i = – D i  ∇c i + -------- c i ∇φ l + c i u
 RT 

The above expressions for the n species i, together with the Poisson equation, give a
set of n+1 equations in n+1 unknowns. These are the Nernst-Planck-Poisson
equations. They can be defined in COMSOL Multiphysics by coupling Transport of
Diluted Species with Electrostatics, but they are highly nonlinear and difficult to
converge. Most often, further approximations can simplify the problem without
compromising accuracy.

• Theory for the Transport of Diluted Species Interface

• Theory of Electrostatics in the COMSOL Multiphysics Reference
Manual

An important dimensional quantity occurring in the Poisson equation is:

RT ε 0 ε s
xD = ------------------
-
2
F I

This is the length across which electric fields are screened. It is called the Debye length.
This is a very short length in electrolyte solutions: for a typical ionic strength, it is of
the order of 1 nm. Electroneutrality holds at distances much larger than 1 nm from a
charged surface:

 zi ci = 0

The constraint of electroneutrality can be used as a condition determine the electric

potential in the Nernst-Planck equations, in place of the full Poisson equation. The
Nernst-Planck equations with electroneutrality are used to describe current flow in the
Tertiary Current Distribution, Nernst-Planck interface.

The Tertiary Current Distribution, Nernst-Planck Interface

34 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

The current flow itself is given by:

il = F  zi Ni
From substitution of the Nernst-Planck expressions for Ni, the laws of conservation of
mass and charge combine to automatically satisfy conservation of current.

We can simplify the system further by considering the arising expression for il in more
detail:

2
F
 Di zi ∇ci – --------
RT l  i  zi ci
2
il = – F ∇φ z Di ci + u

Clearly, the right-most term is zero: that is, convection of an electroneutral solution
does not cause current flow. The left-most term (diffusion current) also vanishes due
to electroneutrality if the gradients of the charge carrying species are zero.

Even if this is not the case, however, this term is often much smaller than the central
term (migration current), so long as the concentrations of the current-carrying ions do
not vary markedly through the solution. Under conditions where the composition of
the electrolyte can be considered nearly constant and current-carrying ions are not
significantly depleted, the diffusion current can be assumed to contribute negligibly.

Hence, it follows that:

i l = – σ l ∇φ l

This expression for current density is used in the Secondary Current Distribution
interface, and also the Primary Current Distribution interface. The difference between
these interfaces lies in the treatment of the electrode-electrolyte interfaces (see Kinetics
of Electrochemical Reactions below). From the above, the conductivity of the
electrolyte σl is given as:

2
F
 zi
2
σ l = -------- Di ci
RT

So long as this quantity does not vary markedly through the solution, the
approximation of zero diffusion current is good. If the diffusivities and concentrations
can be taken as constant, we can approximate that:

2
2F ID mean
σ l ≈ -----------------------------
RT

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 35

 The advantage of the ohmic expression for current density is that it is a linear relation
of current density to electrolyte potential. It is only weakly nonlinear if σl is allowed to
depend on a concentration solved for in a species transport interface. By comparison,
the Nernst-Planck equations with electroneutrality can be highly nonlinear.

The approximations used to derive the secondary current distribution expression place
tighter constraints on the allowed system configurations, however. The ionic strength
of the solution must remain near-constant for the constant conductivity approximation
to be valid. Usually this is only the case for relatively high conductivity solutions.

When the conductivity is large with respect to the current drawn, the electric field
becomes negligible in solution. For negligible electric fields, a diffusion-only
approximation may be used, where E = 0. This converts the Nernst-Planck equations
into Fick’s laws, with a term for convective transport where necessary. Fick’s laws with
convection and electrochemical boundary conditions are solved for in the
Electroanalysis interface.

Even if you think a problem will involve the full Nernst-Planck equations,
it is best to set the model up in Secondary Current Distribution first, in order
to identify any other possible complications in the system while using a
simpler electrochemical model.

Theory for the Current Distribution Interfaces

Modeling Electrochemical Reactions

Electrochemical reactions are defined by using Electrode Reaction or Porous Electrode
Reaction nodes. An electrode reaction is defined by its thermodynamics, kinetics, and
stoichiometry. The latter describes the mass fluxes, sources and sinks arising due to a
certain current density of the reaction.

THERMODYNAMICS OF ELECTROCHEMICAL REACTIONS

An electrolytic reaction involves the exchange of electrons with the electrode. Such a
reaction is written as reduction, even if the reaction occurs predominantly in the
oxidative direction. For example:

+ -
Ag (aq)+e ↔ Ag(s)

36 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

This reaction is called a “half-cell” reaction, since it will occur at a specific
electrode-electrolyte interface. It cannot occur in isolation, but only when coupled to
another half-cell reaction within a two-electrode electrochemical cell. Each reaction
has a characteristic Gibbs energy change that determines whether or not it is
thermodynamically favorable. A negative Gibbs energy change means that the reaction
proceeds spontaneously — it is thermodynamically “downhill”.

The Gibbs energy change is related to the equilibrium potential difference from the
electrode to the electrolyte according to:

ΔG m
E eq, m = – -------------
nm F

where Eeq,m is the potential difference on some external reference scale for which the
reaction is at equilibrium (ΔG = 0). This is called the equilibrium potential or
reduction potential (or in corrosion, corrosion potential) of the electrochemical
reaction, and its absolute value depends on the choice of reference electrode.

Equilibrium potentials should always be quoted versus a specific

reference. If a different reference scale is used in different parts of your
model, the thermodynamics of the system may not behave as expected.

From the standard thermodynamic relation

ΔG = – RT ln K

it follows

RT
E – E eq = -------- ln K
nF

This is the Nernst equation which is a universal thermodynamic expression. It is always

true of systems at thermodynamic equilibrium; it does not necessarily apply to systems
not at equilibrium.

Assuming that the species are ideal and that activity effects can be treated as constant,
then for the conversion between unimolecular reduced and oxidized species:

[Ox] = [Red] exp   -------- ( φ s – φ l – E f )

nF
RT

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 37

 Hence at equilibrium, the concentrations of reactants and products at the
electrolyte-electrode surface are related by an expression which depends on the
potential difference between the two phases, and two reaction parameters: n, the
number of electrons transferred per molecule reduced; and Ef, the formal reduction
potential of the reaction measured on the same potential scale as the
electrode-electrolyte potential difference.

The quantity

η m = φ s – φ l – E eq, m

is known as the overpotential and is particular to a specific reaction occurring at the

interface.

η depends on both the electric potential in the electrode φs and the

electrolyte potential φl. Where there is substantial resistance to current
flow through a solution, the corresponding potential difference in φl,
called ohmic drop, alters the position of the electrochemical equilibrium.
Additional applied potential in the electrical circuit may then be needed
to drive an equivalent overpotential.

KINETICS OF ELECTROCHEMICAL REACTIONS

The Nernst equation tells us the position of equilibrium of a reaction. However, it tells
us nothing about how fast the system may get there. If there is a kinetic limitation —
that is, if the reaction proceeds slowly — the equilibrium condition may never be
observed. As a familiar example, diamond is thermodynamically unstable with respect
to reacting to form graphite at room temperature and pressure. However, this reaction
is kinetically limited by a vast activation energy for the reorientation of atoms, such that
it is never in practice observed, and diamond is technically described as metastable.

We encounter the same issue in many electrochemical contexts. Reactions are

prevented from proceeding to their equilibrium by kinetic limitations. Indeed,
overcoming the natural kinetic sluggishness of the surface reactions of small, nonpolar
molecules such as hydrogen and oxygen is key to much fuel cell research.

There are two important expressions describing the current density due to an
electrochemical reaction as a function of the overpotential and the concentrations of
reactant and product. It should be noted that the validity of these expression is not
general and can never replace experimental kinetic data if such is available.

38 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

The first is the Tafel law which describes an irreversible anodic or cathodic process:

log  ---- = Aη
i
i0

The constant A is the Tafel slope and has units 1/V. It is usually close to a half-integer
multiple of F/RT and is less than or equal to nF/RT. Note that a reference exchange
current density i0 must be specified for the reaction. This is by definition the current
density drawn at zero overpotential.

The Tafel law assumes that a reaction is irreversible. If the reverse reaction
might occur in practice, Tafel kinetics will not be correct.

The second expression is the Butler-Volmer equation which describes a reversible

process, so that either anodic or cathodic current may flow depending on the sign and
magnitude of the overpotential:

α a Fη – α c Fη
i = i 0  exp  --------------- – exp  ----------------- 
RT RT

The Butler-Volmer equation is the most general description of electrode kinetics. It is

highly adaptable because:

• i0 is an empirical quantity.
• It agrees with the Nernst equation when i = 0, so for a very fast reaction ( i 0 → ∞ )
then the Butler-Volmer equation gives the same potential difference as the Nernst
equation. This is equally true under high resistance conditions.
• It agrees with the Tafel equation when either the anodic or cathodic term
dominates. For highly irreversible reactions (very low i0), appreciable current is only
drawn for large overpotential, so this is typically the case.

For a discussion on the Butler-Volmer expression and concentration changes of the

participating species, see the Defining Concentration Dependent Butler-Volmer
Kinetics section below.

For a reversible reaction at very low overpotential (η of order RT/F ~ 25 mV), the
exponentials in the Butler-Volmer equation can be linearized:

( α a + α c )F
i loc = i 0  ---------------------------- η
RT

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 39

 Using a linearized Butler-Volmer reaction can be advantageous when
investigating convergence issues of a model.

The linearized Butler-Volmer equation is not correct for applied

overpotentials larger than (RT / F). This is about 25 mV at room
temperature. It is not suitable outside this range and therefore its use is
confined to electrochemical processes occurring exclusively at low current
density, such as electroplating or electrochemical impedance spectroscopy.

Electrode Kinetics Expressions

FLUXES AND SOURCES/SINKS DUE TO ELECTRODE REACTIONS

Electrode reactions will result in a molecular flux of reacting species to or from the
electrode surface. If you are including mass transport in your model it is common to
couple the flux of a reacting species on a boundary to the electrode reaction current
density (by the Faraday’s law of electrolysis).

The coupling of chemical flux to electric current density is automated in some of the
Electrochemistry interfaces by defining the reaction stoichiometry in the Electrode
Reaction and Porous Electrode Reaction nodes. In the Chemical species transport
interfaces the coupling however need to be set up manually by the Electrode Surface
Coupling nodes. When modeling porous electrodes, the corresponding coupling node
to create a source/sink a domain is the Porous Electrode Coupling node.

The mathematical treatment can be summed up by the expression:

ν jm i m
N j = – ----------------
nm F

This means that the flux Nj of chemical species j into the surface is proportional to the
current density im due to reaction m drawn at an electrode-electrolyte interface. The
constant of proportionality is the stoichiometric number for the species divided by n,
the number of electrons transferred per mole of reactant, in a reductive direction and
F the Faraday constant (96485 C/mol, the absolute charge on a mole of electrons).

40 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

As such, knowledge of the stoichiometry of an electrochemical reaction allows the local
flux of a chemical species to be coupled to the current density contributed by that
reaction. Note that multiple reactions may take place simultaneously at an electrode,
and their contributions to the current density are simply summed.

The stoichiometric coefficients of the chemical species in an

electrochemical reaction are conventionally written with the forward
reaction in the direction of reduction, even if in practice within the system
the reaction predominantly proceeds in the other direction.

COMSOL Multiphysics uses the standard convention that anodic

(oxidative) current is positive. Cathodic (reductive) current is negative.

DEFINING CONCENTRATION DEPENDENT BUTLER-VOLMER KINETICS

If the concentrations at an electrode surface change, this will have an impact on the
local kinetics. The Butler-Volmer kinetics expression is derived by considering the rate
of a redox reaction

-
Ox + ne ↔ Red (2-1)

as the sum of the forward and backward rates according to:

i loc α a FE α c FE
r = -------- = k fwd c R exp  --------------- – k rwd c O exp  – --------------- (2-2)
nF  RT   RT 

where kfwd and krwd are reaction rate constants and cO and cR are the activities of the
oxidized and reduced species of the redox couple, respectively. The potential E is here
defined as

E = φs – φl (2-3)

and the transfer coefficients are equal the sum of electrons in the charge transfer
reaction according to

αa + αc = n (2-4)

By defining an equilibrium potential at which the forward reaction and backward

reaction rates are equal, Equation 2-1 can be shown to be equivalent to the commonly
used Butler-Volmer equation:

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 41

 α a Fη α c Fη
i loc = i 0  exp  --------------- – exp  – --------------  (2-5)
 RT  RT  

In this formulation the exchange current density, i0, is defined as:

α ⁄ n αa ⁄ n
i 0 = i 0, 0 c Rc cO (2-6)

where i0,0 is the exchange current density at standard conditions.

The overpotential is here defined as

η = E – E eq (2-7)

where Eeq is the equilibrium potential is defined by the Nernst equation as

RT c R
E eq = E eq, 0 – -------- ln ------ (2-8)
nF c O

and Eeq,0 is the equilibrium potential at standard conditions.

Note that in Equation 2-5 both i0 and Eeq are concentration dependent. This has some
numerical drawbacks when modeling electrochemical cells including mass transport,
since for low concentrations of the participating species (that is, when c O → 0 or
cR
c O → 0 ), the factor ln ------ may get undefined during the solution process. An
c
expression of the form of O Equation 2-2 is more desirable since this expressions contains
a simple linear dependence on the species activities.

A common solution to this issue is to rewrite the Butler-Volmer expression by defining

the overpotential with respect to a fixed reference state for the activities cR, ref and cO,
ref (typically corresponding to the inlet or initial concentrations), resulting in

cR α a Fη ref cO α c Fη ref
i loc = i 0, ref  ------------- exp  -------------------- – -------------- exp  – -------------------  (2-9)
 c R, ref  RT  c O, ref  RT  

where

α ⁄n α ⁄n
i 0, ref = i 0, 0 c Rc, ref c Oa, ref (2-10)

and

η = E – E eq,ref (2-11)

with

42 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

 RT c R, ref
E eq,ref = E eq, 0 – -------- ln -------------- (2-12)
nF c O, ref

Note that Equation 2-9 now contains a linear dependence on the activities cO and cR.

Double Layer Capacitance

The Tafel and Butler-Volmer expressions can be used to calculate the magnitude of the
current due to electrolysis: this is called faradaic current. However, the
electrode-electrolyte interface may also draw capacitive current due to the attraction
or repulsion of ions creating an oppositely charged layer of ions to form in solution
close to the electrode.

The layer of charge on the electrode and layer of opposite charge in the adjacent
electrolyte is called the double layer and can be thought of as behaving like a parallel
plate capacitor, since the absolute amount of charge it separates varies with the charge
density on the electrode, and hence with its voltage. The physics of double layer
structure and formation are highly complex and are not yet well understood. One of
the simplest empirical methods to account for the observed influence of capacitance
on polarization curves is to introduce a constant ideal capacitance across the
electrode-electrolyte interface.

This effect can be added to via the Double Layer Capacitance condition. The capacitor
stores a surface charge density Q = C d ( φ s – φ l ) , and contributes a dynamic charging
current density (non-faradaic current) equal to iNF = dQ/dt. The total current
recorded in a real experiment equals:

i tot = i Far + i NF

Sometimes in electroanalysis a blank scan with no electrolysis is run to subtract

non-faradaic current. If double layer capacitance is ignored in your model, you should

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 43

 make sure that you are comparing it to experimental data recorded under the same
conditions.

The ability of COMSOL Multiphysics to model electrostatics and

transport of charged species make it tempting to incorporate the double
layer explicitly to add more detail to a model. These coupled equations are
always extremely nonlinear and convergence is not trivial except in the
simplest cases. Although the diffuse double layer can be modeled in
isolation (see example), this is not recommended in conjunction with a
fuller electrochemical model.

Double Layer Capacitance

Porous Electrodes
A porous electrode is one in which the three-dimensional structure of the electrode is
permeable to electrolyte. The electrode-electrolyte interface then extends over a much
larger surface area. This specific surface area (“SSA”, area per unit volume, units 1/m)
is a key property of a porous electrode. Additionally, such an electrode can conduct
electrical current independently through its electrode and electrolyte domains.

Most electrochemical interfaces in COMSOL Multiphysics include Porous Electrode

domain nodes that can be used to model the above situation. In a Porous Electrode,
current density is carried in both the electrode and in the pores which are assumed to
contain electrolyte. For gas diffusion electrodes where the solid is conducting but the
pore phase is not, the Electrode condition should be used.

It is common to combine an electrochemical interface with other physics, in order to

model the mass transport, heat transfer and flow properties of a porous medium. For

44 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

instance, Secondary Current Distribution might be coupled to Transport of Diluted
Species in Porous Media, Heat Transfer in Porous Media and Darcy’s Law.

Homogenized transport parameters such as diffusion coefficients are

commonly obtained for a bulk solution of the material. In porous media
these must be corrected for tortuosity and porosity. Carefully consider
such effects when defining your material properties.

Porous Electrode Theory

Boundary Conditions for Running and Controlling Electrochemical

Cells
An electrochemical cell is typically operated by controlling either the cell voltage
(potentiostatic control) or the cell current (galvanostatic control). In a lab experiment
this is accomplished by using a potentiostat.

In a model, potentiostatic control is defined by using fixed potential boundary

conditions. This can be done by setting the Electric Potential vs ground to control the
cell potential, or the Electrode Potential vs a reference potential somewhere in the
system. Galvanostatic control can be accomplished using Total Current or Average
Current Density boundary conditions. For both cases, one electrode in the cell needs to
be grounded.

Mathematically, a Total Current or Average Current Density condition implies setting the
potential of a boundary to be equal to an additional extra global potential degree of
freedom (floating potential) to comply with the specified current condition. For this
reason, solving for galvanic control is numerically slightly more complex.

Note that explicitly prescribing the current density distribution on an electrode

boundary is hard to accomplish in a real world experiment. In higher dimensions than
1D, Electrode Current Density and Electrolyte Current Density boundary conditions
should be used with care.

SHORT-CIRCUITING A CELL AND GALVANIC CORROSION

The simplest way to model a short-circuited cell is to set both electrodes to the same
(electronic) potential, using a fixed potential boundary condition. The charge balance

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 45

 equation of the electrolyte will make sure the total current over all electrode surfaces
sums up to zero.

Note that many galvanic corrosion situations are practically equivalent to a short circuit
of two electrodes consisting of different metals. In such models, the two metals are set
to the same potential. Usually this potential is chosen to be zero (ground).

• Electrode Potential
• Reference Electrode

Modeling Cyclic Voltammetry

In a cyclic voltammetry experiment, a potentiostat is used to sweep the voltage at the
working electrode linearly from a start potential to a vertex potential, and back again.
Typically, the potential window is chosen to span the formal potential of a redox couple
of interest, allowing both the kinetics and transport properties of the chemical species
to be investigated. The target species reacts under kinetic control to the point of
depletion where the current becomes transport-controlled.

The built-in Cyclic Voltammetry study step in the Electroanalysis interface can be used
to automatically set up the voltage sweep in a time-dependent study.

Common Simplifications when Modeling Electrochemical Cells

SHOULD I MODEL IN 3D OR CAN I MODEL IN 1D?

Many electrochemical systems use repetitive unit cells of high aspect ratio. In these
cases, the lumped effect of edge phenomena in the system will be small. For example,
in fuel cells or batteries it is often possible to use one-dimensional geometries with little
loss of detail. Consider also any mirror or rotational symmetries. Reducing the
geometry dimension where possible, either exactly or approximately, will reduce the
meshing and solving time significantly.

Starting with a 1D model helps to understand the influence of different

reactions and phenomena in an electrochemical system, and gives a good
first estimate of current-voltage behavior.

46 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

NEGLECTING THE CHARGE TRANSFER AND POTENTIAL GRADIENTS IN
ELECTRODES
The voltage over the surface of an electrode is typically constant — or very nearly
constant — since it is a good conductor. This implies that it is either the intrinsic
resistance of the electrolyte or the rate of the electrochemical reaction at the
electrode-electrolyte interface that controls the amount of current drawn in an
electrochemical cell. On the assumption of a constant surface voltage, the electrode
domain itself need not be modeled, and the coupling of charge and mass transport at
its surface treated by an Electrode Surface node.

Electrode Surface

However, when modeling porous and gas diffusion electrodes the metal phase
potential is need typically to be included since the conductivity of the metal phase
potential can be much lower in this type of electrodes. This is done in the Porous
Electrode nodes.

HALF-CELL MODELS
Often, an investigator is only interested in the chemistry taking place at one electrode
in a cell. A model of one electrode is called a “half-cell model”.

This would correspond to an experimental situation where the electrode of interest —

be it anode or cathode — is classified as the working electrode, and the other electrode
is called the counter electrode.

One usually ignores the kinetics of the counter electrode in a model; commonly it is
represented by a constant potential boundary condition. Such a model is only valid if
the counter electrode can draw arbitrarily large amounts of current compared to the
working electrode, so that it never limits the current flow in the electrochemical cell.

REPLACING THIN LAYERS WITH BOUNDARY CONDITIONS

When considering a layer that is very thin compared to other dimensions in the
geometry, it is usually correct to treat that layer using a physical condition, rather than
meshing it.

One important example is the catalyst layer in a fuel cell. Since this layer is only
nanometers in size, transport across it is very fast compared to other parts of the

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 47

 system. Hence, it is not necessary to resolve a distribution of concentrations or
potentials through the layer.

Another example is the passivation layer on an oxidized electrode surface, for which
the “Thin Film Resistance” setting can be used. Because the layer is much thinner than
its surroundings, the electric field through it is almost constant. Therefore, an ohmic
expression can be substituted to create a boundary condition with a potential drop.
This is much more efficient than meshing a geometrically narrow layer.

Film Resistance

INFINITE ELEMENTS FOR STEADY-STATE ELECTROANALYSIS

For microelectrodes, the diffusion profile may approach a steady state whose size is
much larger than that of the working electrode of interest. In such an example, it is
preferable to circumscribe the simulation space to a region not more than about
twenty-five times the electrode size - assuming that the surrounding electrolyte is
uniform. Applying a bulk boundary condition such as a fixed concentration at this
finite distance causes inaccuracy in the solution, however.

It is better to use a layer of Infinite Elements around the finite simulation space to
project the simulation space to infinity, eliminating any error from artificially limiting
the simulation space. This is a typical approximation when the electrolyte domain is a
few orders of magnitude larger than the electrode: for example, a microelectrode in a
cm-scale reaction vessel.

Infinite Elements, Perfectly Matched Layers, and Absorbing Layers in the

COMSOL Multiphysics Reference Manual

Before You Start Building Your Model

INTRODUCING COMPLEXITY ONE STEP AT A TIME

The true art of modeling is knowing what phenomena to include and what phenomena
to neglect. Building complexity in a model by adding one additional piece of physics

48 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

or geometric feature at a time is usually the fastest way to reach the modeling goal.
Here are some general tips:

• Start thinking about your cell in the lowest possible dimension. Starting with a 1D
model helps to understand the influence of different reactions in an electrochemical
system, and gives a good first estimate of current-voltage behavior. Go from 1D to
2D, then from 2D to 3D.
• Every electrode reaction adds numerical nonlinearities to your model. If you have
multiple electrode reactions, add them one at a time.
• Start with a simple description of the electrolyte current, such as Secondary Current
Distribution. Analyze the results to ensure that the electrochemical model is
consistent. Switch only to more complex electrolyte models, or add extra physics
such as mass transfer, heat transfer or flow, only if deemed necessary and when
satisfied with the results from a simpler case.
• If you are including flow in your model, solve for the flow field first before coupling
flow and electrochemistry together.

MODELING CHECKLIST
• Identify which domains are electrode and electrolyte. How will their conductivity
be assessed?
• What is happening on the electrode-electrolyte interfaces? Do both the anode and
the cathode need to be modeled? Do either need to be modeled as domains, or can
they be treated as boundaries?
• What electrochemical reactions take place at the electrode surfaces to cause charge
transfer? Can you parameterize their thermodynamics? Do you know the
equilibrium potentials? Can you parameterize their kinetics — and are the kinetics
ever going to be important? If not, ignore them.
• What is the system reference potential used to quote equilibrium potentials? Where
is the system ground?
• Are charge carriers in the electrolyte plentiful with respect to the drawn current
density, or is charge depletion important? Be aware of nonlinear effects that may
make convergence more difficult.
• If you are performing a time-dependent study, do your initial conditions have a
consistent current-voltage relationship?
• What other physics interfaces need to be coupled? How does charge transfer
influence these physics interfaces?

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 49

 Meshing Advice
The default triangular (2D) or tetrahedral (3D) mesh is normally suitable for solving
the equations describing conservation of charge and mass for an general
electrochemical problem.

Electrochemical models involving mass transport generally benefit from a finer mesh
at the electrode surfaces, and at singularities such as the boundary between an
electrode surface and an insulating surface. This may be accomplished by adding
additional Size mesh nodes for these boundaries only. Also, consider refining the
“element growth rate”, and/or using boundary layer meshing in 3D.

Sometimes, a regular Mapped mesh can be more appropriate in a rectangular (2D)

domain; such domains are common in cutaway schematic studies of batteries and fuel
cells. Similarly the Swept mesh is often appropriate for very thin layers in a 3D model.

For fluid domains, the default physics-controlled mesh should be used, with boundary
layers as required.

For some problems with a stationary flow velocity field and time-dependent
convection of electrochemically reacting species, it may improve convergence to set up
a refined mesh without boundary layers for the species transport study step.

Meshing in the COMSOL Multiphysics Reference Manual

Solving Electrochemical Models

Due to the highly nonlinear nature of electrode kinetics, some electrochemical models
can be difficult to solve. This section includes some general tips and tricks to facilitate
model solving, trouble shooting, and to improve solution accuracy.

GENERAL CURRENT DISTRIBUTION PROBLEMS

Start with the following suggestions if you encounter difficulty solving a problem.

• Make sure that the potential levels are “boot-strapped” somewhere in the model,
preferably by grounding one electrode. If there is no potential level defined
anywhere in the model, your model may have infinitely many solutions, and the
model will not converge.

50 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

• Consider using a Stationary with Initialization or a Time Dependent with Initialization
study. Both these studies will use a Current Distribution Initialization study step as a
first step to solve for the potentials only. If you run into problems solving for the
second step in this study you may have to change the “Current distribution type”
setting to Secondary on the Current Distribution Initialization study step node, and
also review the Initial Values as described in the next bullet.
• Review the Initial Values, especially the potentials. Suitable initial potential values can
usually be derived making a “potential walk” through the geometry, starting at the
grounded boundary. Compute electric and electrolyte potentials in other domains
by assuming equilibrium potential differences between electrode and electrolyte for
the main electrode reactions.
• Switch to Linearized Butler-Volmer kinetics (or a Primary current distribution) while
troubleshooting. This can be useful to help achieve a solution for a model that does
not solve with nonlinear kinetics, thereby indicating suitable initial values for the
nonlinear problem.
• If your model contains porous electrodes, try refining the mesh resolution in these
domains, especially toward the electrolyte boundaries.

• Electrochemistry Interfaces
• Specifying Initial Values and Meshing Techniques in the COMSOL
Multiphysics Reference Manual

ELECTROCHEMISTRY COUPLED TO MASS TRANSPORT

If the model involves electrochemistry coupled to mass transport, here are a few things
to try to help improve model convergence.

• Review the Initial Values for the concentration values. Zero initial concentration
values can be unsuitable for tertiary current distribution problems and battery
simulations, since they could imply that no charge carriers or no reacting material is
present.
• If steep concentration gradients are expected close to electrode surfaces, use
boundary layer meshing or finer mesh Size settings at these boundaries.
• When setting up user-defined kinetics expressions, avoid evaluating negative
concentrations by using expressions such as max(c, eps^2), where eps is the
machine epsilon (a very small but finite number).

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 51

 • Try to solve for low currents and low overpotentials first, then increase the cell load
(for stationary problems this can be done using an auxiliary sweep with
continuation).
• If a problem involving mass transport is hard to solve for high currents, but solves
for low currents, it might be due to mass transport limitations. In this case, review
the transport parameter values and check that the current magnitudes are
reasonable. If the current densities are unreasonably high, review the electrode
reaction settings.
• For time-dependent problems that run into convergence problems after a certain
time, review the solution at the last time-step. If the solution of a reactant reaches
zero or a maximum value (for insertion electrodes in batteries) when the
convergence issues occur, the current load of the model is to high in relation to your
initial concentrations or mass transport properties.

• Electrochemistry Interfaces
In the COMSOL Multiphysics Reference Manual:

• 2D and 3D Boundary Layer Meshes

• Stationary and Parametric Sweep

SETTING UP A STUDY SEQUENCE FOR MULTIPHYSICS PROBLEMS

For multiphysics problems, try to adjust the study sequence.

• Solve certain physics interfaces in a sequence. This can in many cases reduce
computational time and improve convergence. Analyzing the results when solving a
physics interface separately can also help when troubleshooting a nonconverging
model.
• A good strategy is often to solve for the potentials only (that is, disable mass
transport and flow interfaces), using a stationary study step, before solving the full
model in the study sequence. In this way the stationary solution is used as initial
values for the following steps. This can be manually by modifying the settings of the
study node, or in an automated way by using the Stationary with Initialization or Time
Dependent with Initialization study sequences, as described above.
• In many models the flow profile is only slightly (or not at all) affected by changes in
current density. Therefore it can be a good strategy to solve separately for the flow
early in the study sequence, and then solve for the other physics interfaces in the

52 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

 subsequent steps. (If the flow is not affected at all by the current distribution,
solving for the flow can be disabled entirely in consecutive steps.)

• Electrochemistry Interfaces
In the COMSOL Multiphysics Reference Manual:

• Studies and Solvers

• Analyzing Model Convergence and Accuracy
• Achieving Convergence When Solving Nonlinear Equations

TIME-DEPENDENT PROBLEMS WITH LOAD STEPS

For time-dependent problems, try the following to address accuracy and convergence
issues with regards to sudden current or potential load steps.

• Use smoothed current or potential load functions in order to avoid instantaneous

or discrete load steps.
• Add a double layer capacitance to the model, which can improve the numerical
stability.
• Reduce the Maximum step taken by the solver if you want to prevent the solver from
“missing” short square load steps, or change the Steps taken by solver setting from
Free to Strict, or Intermediate, to control the time steps using the Times text field.
Using the Events interface can also be an option in certain cases if the load cycle
itself varies dynamically.

• Double Layer Capacitance

In the COMSOL Multiphysics Reference Manual:

• Step and Time Dependent

• Building a COMSOL Multiphysics Model and The Events Interface

SOLVER SETTINGS
Try adjusting the solver settings.

• In rare cases, try to increase the Maximum number of iterations.

• If you know the order of magnitude of the dependent variables beforehand, setting
the scaling method to Manual for these can improve convergence and the accuracy
of the results. This may be of special importance when solving for concentrations

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 53

 that are initially very small but where the final order of magnitude is know a priori.
This could be the case for the active species in a battery model, for example.

In the COMSOL Multiphysics Reference Manual:

• Studies and Solvers

• Analyzing Model Convergence and Accuracy
• Achieving Convergence When Solving Nonlinear Equations

Electrochemistry Studies and Study Steps and Cyclic Voltammetry in the

COMSOL Multiphysics Reference Manual

In multicomponent systems it is rarely straightforward to predict the rest

potential and direction of current flow. The Current Initialization step in
COMSOL Multiphysics does this for you but is only correct if
concentrations and formal potentials for all electrode reactions are
specified precisely and with respect to a common reference scale.

Electrochemistry Studies and Study Steps in the COMSOL Multiphysics

Reference Manual

Studies and Solvers and Building a COMSOL Multiphysics Model in the

COMSOL Multiphysics Reference Manual

54 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

Postprocessing Your Solution

POTENTIAL VARIABLES
Several different potential variables are available for postprocessing and during
computation. The most common ones are described in Table 2-1.
TABLE 2-1: COMMON POTENTIAL VARIABLES

VARIABLE DESCRIPTION DEFINED AT

phil Electrolyte phase potential Electrolyte and Porous

Electrode domains
phis Electrode phase potential Electrode and Porous
Electrode domains
xxx.phisext Electrode phase potential Electrode Reaction boundaries
to Electrolyte domains
xxx.Eeq_yy Equilibrium potential Electrode Reaction boundaries
and Porous Electrode Reaction
domains
xxx.eta_yy Overpotential Electrode Reaction boundaries

The unit is V for all the above variables.

xxx denotes the tag of the physics interface. For instance, cd for the Secondary Current Distribution inter-
face.
yy denotes the tag of the (Porous) Electrode Reaction node, for instance, er1 for an Electrode Reaction
node.

CURRENT VARIABLES AND CALCULATING THE TOTAL CELL CURRENT

The current density may vary between locations on an electrode surface. This effect is
very important to understand through modeling because it cannot be directly
measured. Experimental measurement can only return the total current drawn at an
electrode, although the variation in current density can be inferred by other means.

To calculate the total current in COMSOL Multiphysics, it is necessary to integrate the

total drawn current density along the boundary or over the domain of the electrode.
Some common current density variables are shown in Table 2-2.
TABLE 2-2: COMMON CURRENT DENSITY VARIABLES.

VARIABLE UNIT DESCRIPTION DEFINED AT

2
xxx.nIl A/m Electrolyte current density in Boundaries to Electrolyte and
normal direction Porous Electrode domains
xxx.nIs A/m2 Electrode current density in Boundaries to Electrolyte and
normal direction Porous Electrode domains

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 55

 TABLE 2-2: COMMON CURRENT DENSITY VARIABLES.

VARIABLE UNIT DESCRIPTION DEFINED AT

xxx.iloc_yy A/m2 Local current density of Electrode Reaction boundaries

electrode reaction
xxx.itot A/m2 Total interface current density Electrode Reaction boundaries
(local sum of all xxx.iloc_yy)
xxx.iv_yy A/m3 Volumetric current density of a Porous Electrode domains
Porous Electrode Reaction
xxx.ivtot A/m3 Total volumetric current Porous Electrode domains
densities (local sum of all
xxx.iv_yy)
xxx.IlMag A/m2 Electrolyte current density Electrolyte domains
magnitude (L2 norm)
xxx.IsMag A/m2 Electrode current density Electrode domains
magnitude (L2 norm)
xxx denotes the tag of the physics interface. For instance cd for the Secondary Current Distribution inter-
face.
yy denotes the tag of the (Porous) Electrode Reaction node, For instance er1 for an Electrode Reaction
node.

In 1D or 1D axisymmetric, the electrode is implicitly uniform so you can just multiply

by the area of the electrode. In 2D or 2D axisymmetric, compute the appropriate line
integral. In 3D, compute the surface integral.

You can also define your own total current variable by using an Integration component
coupling across the electroactive boundaries. This variable can also be used during the
computation. In 1D axisymmetric and 2D axisymmetric components, make sure to
select the Compute integral in revolved geometry check box.

In the COMSOL Multiphysics Reference Manual:

• Component Couplings and Coupling Operators and Integration

Avoid evaluating the xxx.IlMag/xxx.IsMag variables on boundaries. These

are generally less accurate than the xxx.nIl/xxx.nIs variables.

56 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

 3

Electrochemistry Interfaces

This chapter describes the physics interfaces found under the Electrochemistry
branch ( ).

In this chapter:

• The Primary and Secondary Current Distribution Interfaces

• The Tertiary Current Distribution, Nernst-Planck Interface
• Shared Physics Features in the Current Distribution Interfaces
• The Electrode, Shell Interface
• The Electroanalysis Interface
• Theory for the Current Distribution Interfaces
• Theory for Electrochemical Heat Sources
• Theory for the Electrode, Shell Interface
• Theory for the Electroanalysis Interface
• Electrode Potentials and Reference Electrodes
• Solving Electrochemical Models

57
 The Primary and Secondary Current
Distribution Interfaces
In this section:

• The Primary Current Distribution • Electrode Line Current Source

and Secondary Current Distribution • Electrolyte Line Current Source
Interfaces
• Electrode Symmetry Axis Current
• Electrolyte Source
• Initial Values • Electrolyte Symmetry Axis Current
• Porous Electrode Source
• Periodic Condition • Electrode Point Current Source
• Edge Electrode • Electrolyte Point Current Source

Only the physics interface-specific nodes are described here. All other
nodes in the Primary Current Distribution and Secondary Current
Distribution interfaces are described in Shared Physics Features in the
Current Distribution Interfaces

The Primary Current Distribution and Secondary Current

Distribution Interfaces
The Primary Current Distribution (cd) interface ( ) and the Secondary Current
Distribution (cd) interface ( ) are both found under the Electrochemistry
branch ( ) when adding a physics interface.

Primary Current Distribution Interface

The Primary Current Distribution interface defines the transport of charged ions in an
electrolyte of uniform composition as well as current conduction in electrodes using
Ohm’s law in combination with a charge balance. The physics interface neglects
activation overpotentials due to charge transfer reactions.

58 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Use this physics interface to estimate the ohmic losses in simplified models of
electrochemical cells, where the overpotentials of the electrode reactions are small
compared to the ohmic voltage drops in the electrolyte and electrodes.

Secondary Current Distribution Interface

The Secondary Current Distribution interface is similar to the Primary Current
Distribution interface with the difference that it accounts for activation overpotentials.
The relation between charge transfer and overpotential can be described using
arbitrary kinetic expressions, such as Butler-Volmer and Tafel equations.

Use this physics interface for generic modeling of electrochemical cells. It can be
combined with interfaces modeling mass transport to describe concentration
dependent (tertiary) current distributions.

Ohm’s law is used in combination with a charge balance to describe the conduction of
currents in the electrodes and electrolytes.

Use the Current Distribution Type setting on the physics interface node, described
below, to switch between a Primary Current Distribution and a Secondary Current
Distribution interface.

• Introduction to Electrochemistry Modeling

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is cd.

DOMAIN SELECTION

Domains that do not conduct current should be omitted from the

Domain Selection: for example, the gas channels in a fuel cell.

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 59

 OUT-OF-PLANE THICKNESS

For 2D components, enter a value or expression for the out-of-plane

Thickness d (SI unit: m). The value of d determines the size of the domain
perpendicular to the modeled 2D cross section. This value yields, for
example, the correct total current when the current density is obtained
from a 2D simulation.

CROSS SECTIONAL AREA

For 1D components, enter a Cross sectional area Ac (SI unit: m2) to define
a parameter for the area of the geometry perpendicular to the 1D
component. The value of this parameter is used, among other things, to
automatically calculate the total current from the current density vector.
The analogy is valid for other fluxes. The default is 1 m2.

CURRENT DISTRIBUTION TYPE

The Current Distribution Type selected in the list is based on the choice made when
adding a physics interface — Primary or Secondary. The Primary Current Distribution
interface changes to a Secondary Current Distribution interface if the choice is
changed to Secondary, and vice versa.

The selection from this list also governs how electrode reactions are modeled on
interfaces between electrodes and electrolytes.

• Models using a Primary current distribution type use potential constraints (Dirichlet
boundary conditions), according to the equilibrium potential setting.
• Secondary current distribution models use current flux conditions (Neumann
boundary conditions) according to the sum of all electrode reaction current
densities.

DEPENDENT VARIABLES
This physics interface defines dependent variables (fields) for the Electrolyte potential
and Electric potential. The names can be changed but the names of fields and
dependent variables must be unique within a model.

60 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

DISCRETIZATION
To see all settings in this section, click the Show button ( ) and select Advanced
Physics Options.

• Electrochemical Reactions and the Difference Between a Primary and

a Secondary Current Distribution
• Domain Equations for Primary and Secondary Current Distributions
• Shared Physics Features in the Current Distribution Interfaces
• Theory for the Current Distribution Interfaces

Secondary Current Distribution: Wire Electrode: Application Library

path Electrochemistry_Module/Electrochemical_Engineering/wire_electrode

Electrolyte
Use the Electrolyte node to define an electrolyte domain that only conducts current in
the ion conducting phase.

Note that electrolyte in this case does not refer to the pore electrolyte in porous
electrodes (which should be defined by a Porous Electrode node instead).

The Electrolyte conductivity, σl (SI unit: S/m), parameter will define how the current
in the domain depends on the gradient of the potential.

• Domain Equations for Primary and Secondary Current Distributions

• Electrolyte Theory

Initial Values
Use this node to specify the Initial Values of the electrolyte potential and the electric
potential for the solver.

For many electrochemical problems that use nonlinear electrode kinetics, such as
Butler-Volmer kinetics, providing reasonable initial values can significantly improve
solver convergence.

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 61

 A good value for the Electric potential (SI unit: V) in electrode and porous electrode
domains can usually be derived from the boundary conditions. For instance, if a
boundary has been grounded or set to a cell potential, use that value as the initial value
also in the adjacent domain. For the Electrolyte potential (SI unit: V) a good initial
value is often the negative of the equilibrium potential of the grounded electrode.

Porous Electrode
The Porous Electrode node sets up charge balances for the electrode and the pore
electrolyte in a porous electrode. Note that the node should be used for porous
domains that conduct current in both an electrolyte and an electrode phase. For the
case of domains that do not contain a pore electrolyte — for instance, the gas diffusion
layer (GDL) in a PEMFC electrode — use an Electrodenode instead.

Use Porous Electrode Reaction subnodes to define the charge transfer reactions that
occur on the interface between the electrolyte and electrode phases within the porous
electrode. For the Secondary Current Distribution interface, the Porous Matrix
Double Layer Capacitance subnode is also available.

The conductivities are taken From material by default. From the respective material list
you may any material in the model, if present. By default they are set to the Domain
material (which is the material applied to the active domain in the Materials node).

You may use the Effective conductivity correction factors to account for the lowered
effective conductivities of the electrode and electrolyte phases due to the lower volume
fractions of each phase, and the tortuosity of the porous matrix.

FILM RESISTANCE
See the Electrode Surface node.

• Domain Equations for Primary and Secondary Current Distributions

• Porous Electrode Theory

Periodic Condition
Use the Periodic Condition to define a periodic relation between two boundaries—for
instance, in a model describing a repetitive unit cell. For more information, see
Periodic Boundary Conditions in the COMSOL Multiphysics Reference Manual.

62 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Edge Electrode
The Edge Electrode can be used in 3D problems to define electrodes such as long pipes
and thin wires where the electric potential variation within the electrode in the normal
direction to the electrode surface is negligible. This assumption allows for the thin
electrode domain to be replaced by a lumped one-dimensional partial differential
equation formulation on the edge, describing an electrode surface along the edge with
a given Edge electrode radius. In this way the problem size can be reduced, and
potential problems with mesh anisotropy in the thin layer can be avoided.

The electric current conduction in the tangential direction of an edge can be described
by Ohm’s law or a Fixed electric potential or a Floating potential assuming infinite
conductivity of the edge or an External short electric potential which allows to connect
two electrodes over an external connector with a given bulk resistance.

An Edge Electrode can only be applied to edges within, or adjacent to, Electrolyte
domains.

A default Electrode Reaction subnode is added by default to the feature. Double Layer
Capacitance, Electric Ground, Electric Potential, and Electrode Current subnodes can also
be added to the feature.

FILM RESISTANCE
See the Electrode Surface node. The section is only available when a Secondary current
distribution has been selected on the parent node.

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.

The mesh size in the perpendicular direction to the edge should

preferably be in the same order of magnitude as the Edge electrode
diameter in order to achieve good numerical accuracy.

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 63

 Electrode Line Current Source

For 3D components, use the Electrode Line Current Source on edges.

For 2D components use it on points.

For 2D axisymmetric components, it can only be selected on points

outside the symmetry axis.

ELECTRODE CURRENT SOURCE

Enter the Electrode current source ql,s (SI unit: A/m). The default is 0 A/m.

Electrolyte Line Current Source

For 3D components, use the Electrolyte Line Current Source on edges.

For 2D components use it on points.

For 2D axisymmetric components, it can only be selected on points

outside the symmetry axis.

ELECTROLYTE CURRENT SOURCE

Enter the Electrolyte current source ql,l (SI unit: A/m). The default is 0 A/m.

Electrode Symmetry Axis Current Source

For 2D axisymmetric components apply an Electrode Symmetry Axis

Current Source along the symmetry axis boundary.

ELECTRODE CURRENT SOURCE

Enter the Electrode current source ql,s (SI unit: A/m). The default is 0 A/m.

64 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Electrolyte Symmetry Axis Current Source

For 2D axisymmetric components apply an Electrolyte Symmetry Axis

Current Source along the symmetry axis boundary.

ELECTROLYTE CURRENT SOURCE

Enter the Electrolyte current source ql,l (SI unit: A/m). The default is 0 A/m.

Electrode Point Current Source

For 3D components, use the Electrode Points Current Source on edges.

For 2D axisymmetric components, it can only be selected on points

located on the symmetry axis.

ELECTRODE CURRENT SOURCE

Enter the Electrode current source qp,s (SI unit: A). The default is 0 A.

Electrolyte Point Current Source

For 3D components, use the Electrolyte Points Current Source on edges.

For 2D axisymmetric components, it can only be selected on points

located on the symmetry axis.

ELECTROLYTE CURRENT SOURCE

Enter the Electrolyte current source qp,l (SI unit: A). The default is 0 A.

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 65

 The Tertiary Current Distribution,
Nernst-Planck Interface
In this section:

• The Tertiary Current Distribution, • Separator

Nernst-Planck Interface • Reactions
• Electrolyte • Initial Values
• Porous Electrode

Various nodes are also available and described for the Transport of Diluted Species
interface. See Domain, Boundary, and Pair Nodes for the Transport of Diluted Species
Interface

All other nodes in the Tertiary Current Distribution, Nernst-Planck

interface are described in Shared Physics Features in the Current
Distribution Interfaces

The Tertiary Current Distribution, Nernst-Planck Interface

The Tertiary Current Distribution, Nernst-Planck (tcd) interface ( ), found under the
Electrochemistry branch ( ) when adding a physics interface, describes the current
and potential distribution in an electrochemical cell taking into account the individual
transport of charged species (ions) and uncharged species in the electrolyte due to
diffusion, migration and convection using the Nernst-Planck equations. The physics
interface supports different descriptions of the coupled charge and mass transport in
the electrolyte (see Species (Charge Conservation model) below). The electrode
kinetics for the charge transfer reactions can be described by using arbitrary expressions
or by using the predefined Butler-Volmer and Tafel expressions.

Ohm’s law is used in combination with a charge balance to describe the flow of
currents in the electrodes. The charge transfer reactions can be defined as boundary

66 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

conditions or as sources or sinks within a domain in order for the case of porous
electrodes.

Introduction to Electrochemistry Modeling

SETTINGS
The Label is the physics interface node name that will be shown in the model builder
tree.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is tcd.

DOMAIN SELECTION
The domains that do not conduct current should be omitted from the selection list,
for example, the gas channels in a fuel cell.

OUT-OF-PLANE THICKNESS
For 2D components, the Thickness field (default value: 1 m) defines a parameter for the
thickness of the geometry perpendicular to the two-dimensional cross-section. The
value of this parameter is used, among other things, to automatically calculate the total
current from the current density vector. The analogy is valid for other fluxes.

CROSS SECTIONAL AREA

For 1D components, enter a Cross sectional area Ac (SI unit: m2) to define a parameter
for the area of the geometry perpendicular to the 1D component. The value of this
parameter is used, among other things, to automatically calculate the total current
from the current density vector. The analogy is valid for other fluxes. The default is
1 m2 .

SPECIES (CHARGE CONSERVATION MODEL)

The physics interface features four different descriptions of the coupled charge and
mass transport in the electrolyte.

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 67

 Use the Electroneutrality or the Electroneutrality, water based charge conservation
option to model cells with significant concentration gradients of the current-carrying
species (ions). The electroneutrality condition implicitly assumes that all major
current-carrying ions are included in the model. In addition to the electroneutrality
condition, the Electroneutrality, water based option also adds the water auto-ionization
equilibrium condition, including proton and hydroxide transport, when defining the
electrolyte equations. Note that this option adds the concentration variables for
protons (tcd.cH) and hydroxide (tcd.OH) automatically, and that dependent variables
for these two species should not be added under Dependent Variables below.

A Supporting electrolyte describes a situation where the major part of the charge is
transfered by ions whose concentration can be described as constant.

The Poisson option couples the Nernst-Planck equations for mass transport to the
Poisson equation for describing the potential distribution in the electrolyte, without
any assumption of electroneutrality. This option is typically used when modeling
problems where charge separation effects are of interest, typically within nanometers
from an electrode surface.

For the Electroneutrality option, the From electroneutrality list sets the species that is
calculated from the corresponding condition. Note that the choice of species to be
taken from electroneutrality affects the specific boundary conditions that can be set on
the eliminated species. For example, flux and concentration settings cannot be set for
the eliminated species, and initial values cannot be provided. The choice can also have
an impact on the numerics of the problem.

A general advice is to choose a relatively inert ion with high mole fraction to be taken
from electroneutrality for best numerical results.

DEPENDENT VARIABLES
This physics interface defines these dependent variables (fields), the Concentrations of
the species, the Electrolyte potential, and the Electric potential.

The names can be changed but the names of fields and dependent variables must be
unique within a model.

DISCRETIZATION
Concentrations basis function orders higher than Quadratic are not recommended if
transport by convection is dominating in the model.

To see all settings in this section, click the Show button ( ) and select Advanced
Physics Options.

68 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

CONSISTENT STABILIZATION AND INCONSISTENT STABILIZATION
To display these sections, click the Show button ( ) and select Stabilization. There are
two consistent stabilization methods available and selected by default — Streamline
diffusion and Crosswind diffusion. There is one inconsistent stabilization method,
Isotropic diffusion, which is not selected by default. Any settings unique to this physics
interface are listed below.

• When the Crosswind diffusion check box is selected, a weak term that reduces
spurious oscillations is added to the transport equation. The resulting system is
nonlinear. There are two options for Crosswind diffusion type:
- Do Carmo and Galeão — the default option. This type of crosswind diffusion
reduces undershoot and overshoot to a minimum but can in rare cases give
equations systems that are difficult to fully converge.
- Codina. This option is less diffusive compared to the Do Carmo and Galeão
option but can result in more undershoot and overshoot. It is also less effective
for anisotropic meshes. The Codina option activates a text field for the Lower
gradient limit glim (SI unit: mol/m4). It defaults to 0.1[mol/m^3)/tds.helem,
where tds.helem is the local element size.
• For both consistent stabilization methods, select an Equation residual. Approximate
residual is the default setting and it means that derivatives of the diffusion tensor
components are neglected. This setting is usually accurate enough and is faster to
compute. If required, select Full residual instead.

In the COMSOL Multiphysics Reference Manual see Table 2-3 for links
to common sections and Table 2-4 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

• The Nernst-Planck Equations

• Domain Equations for Tertiary Current Distributions Using the
Nernst-Planck Equations and Electroneutrality
• Shared Physics Features in the Current Distribution Interfaces
• Theory for the Current Distribution Interfaces

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 69

 Electrolyte
Use the Electrolyte node to define an electrolyte domain that only conducts current in
the ion conducting phase. The combined charge and mass transfer in the electrolyte is
defined by the node.

What settings are available in this node depends on the Species (Charge Conservation
model) setting, available on the top-node. The Electrolyte conductivity (SI unit: S/n)
setting is only available for the Supporting Electrolyte option. Diffusivity and mobility
settings for H+ and OH- are only available for the Electroneutrality, water-based
option.

The Convection section is available when the Convection check box is selected on the
interface top node. The Velocity field u (SI unit: m/s) of the solvent is specified as a
feature input. Select the source of velocity field from the velocity field list.

By default the Mobility (SI unit: s·mol/kg) for each species is set to be calculated based
on the Diffusion coefficients (SI unit: m2/s) and the temperature using the
Nernst-Einstein relation.

The mobility setting will only have an impact on the transport by migration of charged
species, as defined by the Charge number zc (dimensionless, specify negative charges
using a minus sign). For the Electroneutrality charge conservation model you need at
least one positively and one negatively charged species (ion) in the electrolyte.

Specify the temperature (if you are using mobilities based on the Nernst-Einstein
relation) in the Model Inputs section.

Note that the electrolyte in this case does not refer to the pore electrolyte in porous
electrodes (which should be defined by a Porous Electrode node instead). For porous
separators, use the Separator instead.

• Electrolyte Theory
• Domain Equations for Tertiary Current Distributions Using the
Nernst-Planck Equations and Electroneutrality

Porous Electrode
The Porous Electrode node sets up charge balances for the electrode and the pore
electrolyte in a porous electrode, and as well as the mass balance for the species in the
electrolyte. Note that the node should be used for porous domains that conduct

70 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

current in both an electrolyte and an electrode phase. For the case of domains that do
not contain a pore electrolyte — for instance, the gas diffusion layer (GDL) in a
PEMFC electrode — use an Electrode node instead.

Use Porous Electrode Reaction child nodes to define the charge transfer reactions that
occur on the interface between the electrolyte and electrode phases within the porous
electrode. The Porous Matrix Double Layer Capacitance subnode is also available.

See the Electrolyte node for more information about the Diffusion and Migration in
Electric Field settings of this node.

Correction factors may be specified in the Effective Transport Parameter Correction

section to account for the lowered effective conductivities of the electrode and
electrolyte phases due to the lower volume fractions of each phase, and the tortuosity
of the porous matrix.

FILM RESISTANCE
See the Electrode Surface node.

• Porous Electrode Theory

• Porous Electrode Reactions Theory
• Domain Equations for Tertiary Current Distributions Using the
Nernst-Planck Equations and Electroneutrality

Separator
Use a Separator node to model electrolyte charge and mass transport in an
electronically isolating porous matrix. Use correction factors to account for the
lowered diffusion coefficients in the electrolyte and the lowered conductivities of the
electrode, due to the lower volume fractions of each phase and the tortuosity of the
porous matrix.

See also the Electrolyte node for more information about the Diffusion and Migration in
Electric Field settings of this node.

Reactions
Use the Reactions node to define non-electrochemical reactions in an electrolyte
domain.

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 71

 The node is found from the Additional Sources submenu.

REACTING VOLUME
When specifying reaction rates in the Rc2 (SI unit: mol/m3·s) fields for a species in a
Porous Electrode domain, the specified reaction rate expression may either refer to the
total volume or the pore (electrolyte) volume. For nonporous domains the settings of
the Reacting Volume section has no impact.

For Total volume the reaction expressions are used as specified (multiplied by unity).

For Pore volume this results in the specified reaction expressions being multiplied by
the domain electrolyte volume fraction εl. (εl equals unity for nonporous domains).

Initial Values
Use this node to specify the Initial Values of the concentration, electrolyte potential and
electric potential dependent variables to be used by the solver.

For many electrochemical problems that use nonlinear electrode kinetics, such as
Butler-Volmer kinetics, providing reasonable initial values can significantly improve
solver convergence.

A good value for the Electric potential (SI unit: V) in electrode and porous electrode
domains can usually be derived from the boundary conditions. For instance, if a
boundary has been grounded or set to a cell potential, use that value as the initial value
also in the adjacent domain. For the Electrolyte potential (SI unit: V) a good initial
value is often the negative of the equilibrium potential of the grounded electrode.

For the Concentration initial values, at least one positive and one negative charged
species should have a nonzero and positive initial value (after considering the
electroneutrality condition). The initial value for the ion calculated from the
electroneutrality condition cannot be set explicitly.

Ion Exchange Membrane

Use the ion exchange membrane node to specify a domain with a permanent fixed
space charge. The node is typically used for defining permselective membranes, used
for various applications such as dialysis cells or flow batteries.

The node models the transport of all species added at the interface topnode, and adds
a fixed space charge to the electroneutrality condition.

72 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

The Fixed space charge specifies the charge ions fixed in the membrane polymer matrix.
Use negative space charges for cation selective membranes, and positive charges for
anion selective membranes, respectively.

Select the Apply Donnan Boundary Conditions check box to enable Donnan equilibrium
conditions on all internal boundaries between the domain selected by the node and all
adjacent domains selected by the interface (except Electrode nodes). The boundary
conditions are applied for all species and the electrolyte potential dependent variable.
This option is not available for the Poisson charge conservation model option.

For the Water-Based with Electroneutrality charge conservation model, you need to
select whether to Set potential boundary condition based on the H or OH concentration.
Use H for predominantly acidic electrolytes and OH for predominantly basic
electrolytes.

For the remaining settings of this node, see the Electrolyte and Separator nodes.

Ion Exchange Membrane Boundary

The ion exchange membrane boundary node to specifies an external boundary over
which the flux of a charge carrying species is continuous but the electrolyte potential
shifts with a specified value. This condition is typically used in electrochemical cells
containing both free electrolytes and ion exchange membranes, for instance in dialysis
or flow battery problems. The node is typically used to couple two separate current
distribution interfaces, where one of the interfaces models free electrolyte domain, and
the other interface models the ion-exchange membrane domain.

Note that using the Ion Exchange Membrane domain node often is a more convenient
modeling approach if the transported species in the free electrolyte and ion exchange
membrane are the same.

The node is applicable to external boundaries to electrolyte domains.

The choice of Charge-carrying species concentration species specifies that the current
flowing over the boundary will be carried by this species (which must have a nonzero
charge number). Use the Membrane potential setting to set the electrolyte potential on
the membrane side of the boundary. Note that if this potential is set to the electrolyte
potential of a Primary or Secondary Current Distribution interface, no additional
settings are needed in that interface to set up the correct boundary condition.

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 73

 The potential condition may be either Donnan, which will calculate the potential shift
over the boundary based on the membrane charge carrying species concentration, or
can be User defined.

74 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Shared Physics Features in the
C ur r e nt D i s t r i b u t i on In t erfaces
Domain, Boundary, Pair, Edge, and Point Nodes for the
Electrochemistry Interfaces
Electrochemistry Interfaces interfaces have these domain, boundary, edge, point, and
pair nodes, listed in alphabetical order, available from the Physics ribbon toolbar
(Windows users), Physics context menu (Mac or Linux users), or right-click to access
the context menu (all users).

Most nodes and features described in this section are available for all the
Electrochemistry branch interfaces unless otherwise indicated.

In general, to add a node, go to the Physics toolbar, no matter what

operating system you are using. Subnodes are available by (right) clicking
the parent node and selecting it from the Attributes menu.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 75

 • Double Layer Capacitance • Electrolyte Current Density
• Circuit Terminal • Electrolyte Current Source
• Electric Ground • Electrolyte Potential
• Electric Potential • External Short
• Electric Reference Potential • Harmonic Perturbation
• Electrode • Insulation
• Electrode Current • Internal Electrode Surface
• Electrode Current Density • Line Mass Source1
• Electrode Current Source • Point Mass Source1
• Electrode-Electrolyte Boundary • Porous Electrode Reaction
Interface • Porous Electrode Reaction
• Electrode Potential • Porous Matrix Double Layer
• Electrode Reaction Capacitance
• Electrode Surface • Reference Electrode
• Electrode Reaction • Symmetry
• Electrode Current
1 For the Tertiary Current Distribution, Nernst-Planck interface, these nodes are

available and described for the Transport of Diluted Species interface.

In the COMSOL Multiphysics Reference Manual see Table 2-3 for links
to common sections and Table 2-4 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Theory for the Current Distribution Interfaces

Electrode
Use the Electrode node to define an electrode domain that only conducts current in
the electron conducting phase.

76 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

The node is typically used for modeling solid metal electrodes, current collectors,
current feeders, gas diffusion layers and gas backings.

The Electrical conductivity σs (SI unit: S/m) parameter will define how the current in
the domain depends on the gradient of the potential.

Electrode Theory

Electrode Current Source

Use the Electrode Current Source node to define contributions to the current density
from electron current sources. The Current source, Qs (SI unit: A/m3), is added
according to the following equation:

∇ ⋅ is = Qs

where

i s = – σ s ∇φ s

and σs denotes the electrode’s conductivity and φ s the electric potential.

To use this feature, click the Show button ( ) and select Advanced Physics Options
then add the node from the Additional Sources submenu.

Electrolyte Current Source

Use the Electrolyte Current Source node to define contributions to the current density
in the electrolyte from, for example reactions, or other effects.

The Current source, Ql (SI unit: A/m3), is added according to the following equation:

∇ ⋅ il = Ql

To use this feature, click the Show button ( ) and select Advanced Physics Options
then add the node from the Additional Sources submenu.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 77

 Porous Electrode Reaction
The Porous Electrode Reaction node defines the electrode kinetics for a charge transfer
reaction that occurs at the interface between the pore electrolyte and the electrode
matrix a porous electrode. The node can be added as subnode to a Porous Electrode
node. Add multiple nodes to the same Porous Electrode node to model multiple
reactions, for instance in mixed potential problems.

See the Electrode Reaction node for a description of the Equilibrium Potential,
Electrode Kinetics, Stoichiometric Coefficients and Heat of Reaction sections.

ACTIVE SPECIFIC SURFACE AREA

The Active specific surface area, av (SI unit: m2/m3) specifies the area of the
electrode-electrolyte interface that is catalytically active for this porous electrode
reaction. av is multiplied by iloc, defined in the Electrode Kinetics section, to produce
a current source in the domain.

This section is not available for primary current distribution interfaces.

• Porous Electrode Reactions Theory

• Electrode Kinetics Expressions.

Porous Matrix Double Layer Capacitance

Use the Porous Matrix Double Layer Capacitance subnode to define a non-faradaic
double layer current density at the interface between the porous electrode matrix and
the electrolyte. The node can be added as subnode to a Porous Electrode node.

The resulting double layer current source in the Porous Electrode domain depends on
the time derivative of the potentials and is proportional to both the Electrical double
layer capacitance Cdl (SI unit: F/m2) and the Double layer area av,dl (SI unit: 1/m).

Note that for stationary problems the double layer current is zero.

This node is not available for the Primary Current Distribution interface.

Use the settings of the Stoichiometry section (not available in the Primary or Secondary
Current Distribution interfaces) to control what species are participating in the double
layer charging — that is, the mass exchange between the double layer and the
electrolyte outside the double layer.

78 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Insulation
The Insulation boundary condition describes the walls of a cell or the boundaries of the
cell that do not face a conductor. The boundary condition imposes the following
equation:

ik ⋅ n = 0

where ik denotes the current density vector and k = l, s is an index for the electrolyte
and electrode, respectively.

Symmetry
For the Primary Current Distribution and Secondary Current Distribution interfaces,
the Symmetry boundary condition is identical to the Insulation condition.

For the Tertiary Current Distribution, Nernst-Planck interface, the Symmetry

boundary condition imposes a no flux condition for the molar flux of species at a
boundary.

Symmetry Theory

Electrode Surface
Use the Electrode Surface node to model an electrochemical electrode-electrolyte
interface between an electrolyte domain and an electrode boundary where the
electrode is not included explicitly as a domain in the model geometry. Set the electric
potential of the electrode or specify a current condition that the potential of the
electrode shall fulfill, and use subnodes to specify the Electrode Reaction and the
Double Layer Capacitance at the interface.

This node can only be applied on outer boundaries to electrolyte domains. For internal
boundaries between electrolyte and electrode domains, use the Internal Electrode
Surface node.

FILM RESISTANCE
Use a film resistance if you want to include an additional potential drop due to an
ohmic resistance at the interface between the electrode and the electrolyte, for instance
due to build-up of insulating deposits.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 79

 Specify either a Surface resistance Rfilm (SI unit: Ω·m2) directly or choose the Thickness
and conductivity option to calculate the surface resistivity based on a depositing film
thickness.

HARMONIC PERTURBATION
Use this section in conjunction with AC Impedance study types to control the
perturbation amplitude in the frequency domain.

The perturbation parameter is either Electric potential, Electrode potential, Total

current, or Average current density, based on the Boundary condition selected in the next
section.

The frequency spectrum is specified in the study node.

BOUNDARY CONDITION
This section specifies the potential in the electrode phase of the electrolyte-electrode
interface. The electrode potential is used (via the overpotential) by the Electrode
Reaction subnodes.

Use the Electric potential option to set the value of the potential explicitly with respect
to ground whereas the Electrode potential will set the potential value with respect to a
reference potential. Total current, Average current density, and External short all add an
extra global degree of freedom for the potential in the electrode phase, set to comply
with the chosen condition.

When using the Total current option in 1D or 2D, the boundary area is based either
on the Cross sectional area (1D), or the Out-of-Plane thickness (2D) properties, set on
the physics interface top node.

See also the documentation for the Electrode Potential and External Short nodes for
further information about these boundary condition.

EQUILIBRIUM POTENTIAL HANDLING (PRIMARY CONDITION)

This setting only has an effect if 1) there are multiple Electrode Reaction subnodes
present and 2) if either a Current Distribution Initialization study step (using a
Primary Current distribution type), or the Primary Current Distribution interface is
used.

The setting determines which equilibrium potential value will be used for defining the
primary current distribution constraint. When the First reaction has been selected, the
first electrode reaction subnode must be active in the model.

80 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

To display this section, click the Show button ( ) and select Advanced Physics Options.

CONSTRAINT SETTINGS
For primary current distributions, the use of weak constraints will in some cases give a
more accurate value of the local current density during the solver process. This may in
turn render more accurate results when coupling to the local current density variable
to describe other phenomena in the model, for instance when modeling geometry
deformation due to electrode dissolution/deposition.

The section is available in the Primary Current Distribution and Secondary Current
Distribution interfaces when the Current Distribution Model property has been set to
Primary.

This section is only available in the Primary Current Distribution and Secondary
Current Distribution interfaces when the Current Distribution Model property has been
set to Primary. To display this section, click the Show button ( ) and select Advanced
Physics Options.

• Electrode Reactions Theory

• Film Resistance

Electrode Reaction
The Electrode Reaction subnode defines the electrode kinetics for a charge transfer
reaction that occurs on an electrolyte-electrode interface boundary. Use multiple
nodes to model multiple reactions, for instance in mixed potential problems.

The parent node may be either an Internal Electrode Surface or an Electrode Surface.

Note that the Electrode Kinetics and Stoichiometric Coefficients sections described
below are not available for all Electrochemistry interfaces.

EQUILIBRIUM POTENTIAL
The Equilibrium potential, Eeq (SI unit: V), is used in the electrode kinetics expressions
in the following section (via the definition of the overpotential), or for setting up
primary current distribution potential constraints.

The Temperature derivative of equilibrium potential parameter, dEeq/dT (SI unit:

V/K), is used when calculating the reversible heat source of the electrode reaction,

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 81

 which in turn can be used for coupling to heat transfer physics. Note that dEeq/dT
parameter value has no impact on the equilibrium potential variable.

ELECTRODE KINETICS
The settings of this section will define the Local current density, iloc (SI unit: A/m2), at
the interface between the electrolyte and the electrode. Note that iloc for all built-in
kinetics expression types will depend on the overpotential, which in turn depend on
the Equilibrium potential defined in the previous section.

For all expressions the Exchange current density i0 (SI unit: A/m2) is a measure of the
kinetic activity.

Butler-Volmer or Linearized Butler-Volmer

These kinetics expression are typically used for secondary current distribution
problems.

The Linearized Butler-Volmer is valid when the overpotentials of the reactions are small
(<<25 mV). The linearized version can also be used to troubleshoot a model with
convergence problems.

The Anodic transfer coefficient, αa (dimensionless), and Cathodic transfer coefficient, αc

(dimensionless), parameters will impact how much iloc will change upon changes in the
overpotential.

Anodic Tafel Equation

This kinetics expression type neglects the cathodic (negative) term in the
Butler-Volmer equation. It is only valid for electrode reactions with high anodic
overpotentials (>>100 mV).

The Anodic Tafel slope, Αa (SI unit: V), defines the required increase in overpotential
to result in a tenfold increase in the current density.

Cathodic Tafel Equation

This kinetics expression type neglects the anodic (positive) term in the Butler-Volmer
equation. It is only valid for electrode reactions with significant cathodic overpotentials
(<<-100 mV).

The Cathodic Tafel slope, Αc (SI unit: V), describes the required decrease in
overpotential to result in a tenfold increase in the current density magnitude. Αc
should be a negative value.

82 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Concentration Dependent Kinetics
This kinetics expression type is typically used in tertiary current distribution problems.
One or both of the Oxidizing species expression CO (dimensionless) and Reducing species
expression CR (dimensionless) parameters may be concentration dependent, and
should typically be defined so that CO = CR at equilibrium.

Fast Irreversible Electrode Reaction

This kinetics expression type is typically used in tertiary current distribution problems
for reactions occurring far away from the equilibrium potential.

The kinetics expression type defines an irreversible electrode reaction where the
kinetics is so fast that the only factor limiting the reaction rate is the transport of a
species to the reacting surface.

The node will set the Rate limiting species concentration to zero at the boundary, and
balance the fluxes of the species participating in the reaction and the current densities
according to the Stoichiometric Coefficients settings.

Thermodynamic Equilibrium (Primary Condition)

This choice imposes a zero overpotential for the electrode reaction by applying a
constraint on the potential variables in order to comply with the equilibrium potential.
Use this kinetics for very fast reactions.

In the Secondary Current Distribution interface the condition set by this expression
type is mathematically identical to what is applied when a Primary Current
Distribution is chosen on the interface top node. The expression type can hence be
used to mix primary and secondary current distributions on different electrodes. The
Thermodynamic equilibrium (primary condition) cannot not be used when defining
the kinetics for multiple electrode reactions at the same electrode in the Secondary
Current Distribution interface.

Limiting Current Density

Use the Limiting Current Density to impose an upper limit on the local current density
magnitude. The feature can be used to model additional mass transport limitations that
are not already included in the local current density expression.

For Limiting Current Density enter a value for ilim (SI unit: A/m2).

STOICHIOMETRIC COEFFICIENTS
Specify the Number of participating electrons nm in the electrode reaction and the
Stoichiometric coefficient (vc1, vc2, and so forth) for each of the involved species
according to the following generic electrochemical reaction:

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 83

  νox Sox + ne  νred Sred
-
⇔ (3-1)
ox red

Set νi as positive (νred) for the reduced species and negative (νox) for the oxidized
species in an electrochemical reaction. The number of participating electrons, n,
should be positive.

If the concentration of a species in the charge conservation model for the electrolyte is
based on an algebraic expression (such as the electroneutrality condition, or the water
auto ionization), the stoichiometric coefficient for this species cannot be set explicitly.
The stoichiometric coefficient will instead be set implicitly, based on the number of
electrons and the stoichiometric coefficients of the other species participating in the
reaction.

An easy way to determine the stoichiometric coefficients for a reaction is

to write the reaction as a reduction reaction (with the electrons on the
left), irrespectively on the expected actual direction of the reaction in the
model. The species on the left side then have negative coefficients and the
species on the right have positive coefficients.

HEAT OF REACTION
The Heat of Reaction section provides two options: Temperature derivative and
Thermoneutral voltage to calculate the reversible heat source of the electrode reaction,
which in turn can be used for coupling to heat transfer physics.

The Temperature derivative of equilibrium potential parameter, dEeq/dT (SI unit:

V/K), can be specified in case of Temperature derivative selection. Note that dEeq/dT
parameter value has no impact on the equilibrium potential variable.

The Thermoneutral voltage parameter, Etherm (SI unit: V), can be specified in case of
Thermoneutral voltage selection.

• Electrode Reactions Theory

• Electrode Kinetics Expressions

84 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Double Layer Capacitance
The Double Layer Capacitance subnode describes the non-faradaic currents due to
charge and discharge of the double layer situated at the interface between the electrode
and the electrolyte. The resulting double layer current density on the boundary
depends on the time derivative of the potentials and is proportional to the Electrical
double layer capacitance Cdl (SI unit: F/m2). For stationary problems the double layer
current density is zero.

Use this node to simulate transient analysis techniques, such as AC-impedance analysis
and current interrupt studies.

The parent node may be either an Internal Electrode Surface or a Electrode Surface.

This subnode is not available for the Primary Current Distribution interface.

Use the settings of the Stoichiometry section (not available in the Primary or Secondary
Current Distribution interfaces) to control what species are participating in the double
layer charging — that is, the mass exchange between the double layer and the
electrolyte outside the double layer.

Internal Electrode Surface

The Internal Electrode Surface node defines the electrochemical electrode-electrolyte
interface between an electrode domain and the electrolyte domain. Use this node as a
parent node for Electrode Reactions and the Double Layer Capacitance of an
electrolyte-electrode interface when you explicitly model the electron conducting
electrode as a domain in your model.

Electrode domain
φs
Electrolyte domain
φl

Internal Electrode Surface

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 85

 The node can only be applied at internal boundaries between electrode and electrolyte
domains. Note that, due to the high conductivity of many electrode materials, an
Electrode domain can many times be replaced an external condition at the electrolyte
boundary. For such cases, consider using the Electrode Surface instead.

For a description of the Film Resistanceand Constraint Settings sections, see the
Electrode Surface node.

• Electrode Reactions Theory

Electrolyte Potential
Add the Electrolyte Potential node from Electrolyte submenus for boundaries, edges,
and points to set a fixed potential at a position in the electrolyte. This node can be used
to model half-cells, or to set the electrolyte potential at the position of, for example, a
reference electrode.

The node sets the potential in the electrolyte, φ l, to be equal to the Boundary
electrolyte potential, φ l, bnd (SI unit: V).

By right-clicking this node you may add a Harmonic Perturbation subnode.

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.

Electrolyte Current
The Electrolyte Current boundary condition sets the total current or average current
density of a boundary. It will set a constant electrolyte potential along the given
boundary, that satisfies the current value setting.

When using the Total current option in 1D or 2D, the boundary area is based either
on the Cross sectional area (1D) or the Out-of-Plane thickness (2D) properties, set on
the physics interface top node.

86 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.

• Electrolyte Current Theory

Electrolyte Current Density

Use the Electrolyte Current Density node to specify the current density distribution
along a boundary.

Note that using this node in 2D or 3D may result in an uneven potential distribution
along the boundary. To mitigate such effects you may use the Electrode Current node
instead.

By right-clicking this node you may enable Harmonic Perturbation. This means that the
node will only be active when solving for Frequency Domain study steps (typically used
in AC Impedance studies). The frequency spectrum is specified in the study node.

Electrode-Electrolyte Boundary Interface

Note that this is an advanced physics feature that is normally not used. To display this
feature in the context menu, click the Show button ( ) on the Model Builder and then
select Advanced Physics Options then add the Electrode-Electrolyte Boundary Interface
node from the Electrode or Pairs>Electrode submenu.

Use this node to model an electrochemical interface between an electrolyte and a

electrode where the electrolyte domain is not included explicitly in the model. The
node can only be applied on outer boundaries to electrode domains. Set the potential
of the electrolyte either explicitly, or specify a current condition that the potential of
the electrode shall fulfill.

Electrode Reaction and Double Layer Capacitance subnodes are available from the
context menu (right-click the parent node) or from the Physics toolbar, Attributes
menu.

This node is available for the Secondary Current Distribution and Tertiary Current
Distribution, Nernst-Planck interfaces.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 87

 BOUNDARY CONDITION
This section specifies the potential of the electrolyte phase for the electrolyte-electrode
interface. The electrolyte potential is used (via the overpotential) by the Electrode
Reaction subnodes.

The Electrolyte potential will set the potential value directly, whereas Total current or
Average current density both add an extra global degree of freedom for the potential in
the electrolyte phase, set to comply with the chosen condition.

When using the Total current option in 1D or 2D, the boundary area is based either
on the Cross sectional area (1D) or the Out-of-Plane thickness (2D) properties, set on
the physics interface top node.

Electric Ground
This node to sets the electric potential to zero.

The node is typically used to ground the voltage at an external boundary in a model
that contains either electrode or porous electrode domains.

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.

Electric Potential
This node sets the electric potential in the electrode (or a porous electrode), φ s, to a
value, φ s, bnd according to the following:

φ s = φ s, bnd

The node is typically used to set the cell voltage at an external boundary in a model
that contains either electrode or porous electrode domains.

By right-clicking this node you may add a Harmonic Perturbation subnode.

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.

Electrode Current Density

The Electrode Current Density boundary condition can be applied at an external
boundary of a model that contains either electrode or porous electrode domains.

88 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Note that using this node in 2D or 3D may result in an uneven potential distribution
along the boundary. To mitigate such effects you may use the Electrode Current node
instead.

By right-clicking this node you may enable Harmonic Perturbation. This means that the
node will only be active when solving for Frequency Domain study steps (typically used
in AC Impedance studies). The frequency spectrum is specified in the study node.

Electrode Current
Use the Electrode Current node to set the total current or average current density over
an external electrode or porous electrode boundary — typically at the interface
between the electrode and the current collector or current feeder. The condition sets
the total current without imposing the current density distribution. The potential
along the boundary is calculated in order to satisfy the total value of the current.

When using the Total current option in 1D or 2D, the boundary area is based either
on the Cross sectional area (1D), or the Out-of-Plane thickness (2D) properties, set on
the physics interface top node.

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options

• Electrode Current Theory

Electrode Power
The Electrode Power boundary condition sets the power drawn from, or inserted to, an
electrical cell at external electrode boundary.

When using the Total power option in 1D or 2D, the boundary area is based either on
the Cross sectional area (1D), or the Out-of-Plane thickness (2D) properties, set on the
physics interface top node.

Electrode Power Theory

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 89

 Harmonic Perturbation
Use the Harmonic Perturbation subnode to specify the voltage amplitude perturbation
in the frequency domain. The harmonic perturbation is only applied when solving for
a Frequency-Domain study type, which is typically used in AC Impedance studies.

The Harmonic Perturbation subnode can be added to the Electric Potential, Electrolyte
Potential. The subnode is available from the context menu (right-click the parent
node) or from the Physics toolbar in the Contextual group.

The frequency spectrum is specified in the study node.

You may also specify harmonic perturbations to the Electrode Current Density,
Electrolyte Current Density and Electrode Surface nodes.

Frequency Domain Perturbation Study Step in the COMSOL

Multiphysics Reference Manual

Electrode Potential
Use the Electrode Potential node to set a boundary condition for the electric potential
with respect to a defined reference potential.

Electric potentials defined by the Electric Reference Potential and Reference Electrode
point nodes can be used as input when specifying the Electric reference potential φ vs,ref
(SI unit: V).

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.

Electrode Potentials and Reference Electrodes

External Short
Use the External Short node to connect two electrodes over an external connector with
a given Resistance R (SI unit: ohm).

90 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

The boundary selected in the External Short node will be set to a constant potential,
φ s, here , and the integrated current over the boundary will be computed according to
Ohm’s law:

φ s = φ s, here

φ s, here – φ s, there
φ s, here :  ( n ⋅ Is )ddΩ = – ---------------------------------------
R
-
dΩ

where φ s, there (V) is the potential of the connected electrode. Use the Connected
Potential list to choose among available connection potentials for the value of φ s, there .

Reference Electrode
The Reference Electrode node is a point feature applicable to electrolyte domains. It
defines a global electric reference potential and can be used in the Electrode Potential
node for setting the electric potential of an electrode boundary with respect to the
reference potential.

EQUILIBRIUM POTENTIAL
See Electrode Reaction for information about the settings of this section.

Electrode Potentials and Reference Electrodes

Electric Reference Potential

The Electric Reference Potential node is a point feature applicable to electrode domains.
It defines a global electric reference potential equal to the electric potential in the point
and can be used in the Electrode Potential feature for setting the electric potential of
an electrode boundary with respect to the reference potential.

Electrode Potentials and Reference Electrodes

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 91

 Circuit Terminal
This feature is only available with an AC/DC Module or a Batteries & Fuel Cells
Module license.

Use the Circuit Terminal node to specify a coupling to the External I vs U node in the
Electrical Circuit interface.

92 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

The Electrode, Shell Interface
The Electrode, Shell (els) interface ( ), found under the Electrochemistry
branch ( ) when adding a physics interface, models electric current conduction in
the tangential direction on a boundary.

The physics interface is suitable for modeling thin electrodes where the potential
variation in the normal direction to the electrode is negligible. This assumption allows
for the thin electrode domain to be replaced by a partial differential equation
formulation on the boundary. In this way the problem size can be reduced, and
potential problems with mesh anisotropy in the thin layer can be avoided.

Ohm’s law is used in combination with a charge balance to describe the conduction of
currents in the shell electrode.

When this physics interface is added, these default nodes are also added to the Model
Builder — Electrode, Electric Insulation (the default edge or point condition), and Initial
Values. Then, from the Physics toolbar, add other nodes that implement, for example,
edge or point conditions and current sources. You can also right-click Electrode, Shell
to select physics features from the context menu.

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is els.

THICKNESS

For 2D components, enter a value or expression for the Out-of-plane

thickness d (SI unit: m). The default value is 1 m.

THE ELECTRODE, SHELL INTERFACE | 93

 DEPENDENT VARIABLES
The dependent variable (field variable) is for the Electric potential. The name can be
changed but the names of fields and dependent variables must be unique within a
model.

DISCRETIZATION
To see all settings in this section, click the Show button ( ) and select Advanced
Physics Options.

• Theory for the Electrode, Shell Interface

• Boundary, Edge, Point, and Pair Nodes for the Electrode, Shell
Interface

In the COMSOL Multiphysics Reference Manual see Table 2-3 for links
to common sections and Table 2-4 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Boundary, Edge, Point, and Pair Nodes for the Electrode, Shell
Interface
The Electrode, Shell Interfacehas these boundary, edge, point, and pair nodes, listed
in alphabetical order, available from the Physics ribbon toolbar (Windows users),
Physics context menu (Mac or Linux users), or right-click to access the context menu
(all users).

In general, to add a node, go to the Physics toolbar, no matter what

operating system you are using. Subnodes are available by clicking the
parent node and selecting it from the Attributes menu.

94 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

These physics nodes are described in this section:

• Boundary Current Source • Electric Potential

• Current Source • External Current Density
• Electrode • Ground
• Electric Insulation • Initial Values
• Normal Current Density

These nodes are available and described for the Current Distribution interfaces, where
edges (3D components) or points (2D and 2D axisymmetric components) are selected
instead of boundaries.

• Electrode Potential
• Electric Reference Potential

For axisymmetric components, COMSOL Multiphysics takes the axial

symmetry boundaries (at r = 0) into account and automatically adds an
Axial Symmetry node to the component that is valid on the axial symmetry
boundaries only.

In the COMSOL Multiphysics Reference Manual see Table 2-3 for links
to common sections and Table 2-4 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Electrode
The Electrode node defines the current conduction in the tangential plane. Use the
node to define the electrode thickness and electrical conductivity.

ELECTRODE
The Electrode thickness s (SI unit: m) defaults to 10−14 m.

The default Electrical conductivity σ (SI unit: S/m) uses values From material. Or select
User defined. For User defined enter values or expressions for an isotropic or anisotropic
conductivity. Select Isotropic, Diagonal, Symmetric, or Anisotropic depending on the

THE ELECTRODE, SHELL INTERFACE | 95

 properties of the electrolyte. To use another type of temperature dependence than a
linear temperature relation, enter any expression for the conductivity as a function of
temperature. Then enter a value or expression in the field or matrix.

Theory for the Electrode, Shell Interface

Initial Values
The Initial Values node adds the electric potential that can serve as an initial guess for
a nonlinear solver. If more than one initial value is needed, add Initial Values nodes from
the Physics toolbar.

INITIAL VALUES
Enter values or expressions for the Electric potential (SI unit: V). The default value
is 0 V.

External Current Density

Use the External Current Density node to define the external current density.

EXTERNAL CURRENT DENSITY

Based on space dimension, enter the vector components (x, y, and z for 3D
components, x and y for 2D, or r and z for 2D axisymmetric components) of the
External current density ie (SI unit: A/m2). The defaults are 0 A/m2.

Current Source
The Current Source node adds a source term to Equation 3-6. Use this node to define
the current source.

ELECTRODE CURRENT SOURCE

Enter a value or expression for the Current source Qi (SI unit: A/m3). The default is
0 A/m3.

96 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Normal Current Density
The Normal Current Density node is applicable to exterior boundaries that represent
either a source or a sink of current. It sets a condition for the current density according
to:

∇T ⋅ is = in

The node can be used to couple the Electrode, Shell interface to the electrode
reactions in an Electrochemistry interface that describes the electrolyte currents in the
adjacent domain.

NORMAL CURRENT DENSITY

Enter a value for the Electrode current source in (SI unit: A/m2). The default is
0 A/m2.

Electric Insulation
The Electric Insulation node is the default edge (3D components) and point (2D and
2D axisymmetric components) condition and describes the edges of the shell
(boundary) that do not conduct electricity.

Boundary Current Source

The Boundary Current Source node is available on edges (3D components) and points
(2D and 2D axisymmetric components) and sets a condition for the current density
according to:

i s ⋅ n = i s, 0

BOUNDARY CURRENT SOURCE

Enter a value or expression for the Inward current density is,0 (SI unit: A/m2). The
default is 0 A/m2.

Ground
The Ground node is available on edges (3D components) and points (all components)
and sets the potential according to φ s = 0 .

THE ELECTRODE, SHELL INTERFACE | 97

 EDGE OR POINT SELECTION

Beware that constraining the potential on edges or points in 3D or on

points in 2D usually yields a current outflow that is mesh dependent.

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.

Electric Potential
The Electric Potential node is available on edges (3D components) and points (all
components) and sets the potential according to φ s = φ s, 0 .

EDGE OR POINT SELECTION

Beware that constraining the potential on edges or points in 3D or on

points in 2D usually yields a current outflow that is mesh dependent.

ELECTRIC POTENTIAL
Enter the value or expression for the Electric potential φ s, 0 (SI unit: V).

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.

98 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

The Electroanalysis Interface
The Electroanalysis (elan) interface ( ), found under the Electrochemistry
branch ( ) when adding a physics interface, has the equations, boundary conditions,
and rate expression terms for modeling mass transport of diluted species in electrolytes
using the diffusion-convection equation, solving for electroactive species
concentration(s). The physics interface contains tailor-made functionality for modeling
cyclic voltammetry and electrochemical impedance spectroscopy.

Use this physics interface to model electroanalytical problems with electrolyte

solutions containing a large quantity of inert “supporting” electrolyte. Ohmic loss is
assumed to be negligible.

The settings for this physics interface can be chosen so as to simulate chemical species
transport through diffusion (Fick’s law), migration (when coupled to an electric field
— electrokinetic flow), and convection (when coupled to fluid flow).

The physics interface supports simulation of transport by convection and diffusion in

1D, 2D, and 3D as well as for axisymmetric components in 1D and 2D. The default
dependent variables are the molar concentrations, c1 and c2, of the two electroactive
species in a redox couple.

Note that most of the physics interface settings are the same as for The Transport of
Diluted Species Interface.

• Introduction to Electrochemistry Modeling

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is elan.

THE ELECTROANALYSIS INTERFACE | 99

 OUT-OF-PLANE THICKNESS
For 2D components, the Thickness field (default value: 1 m) defines a parameter for the
thickness of the geometry perpendicular to the two-dimensional cross section. The
value of this parameter is used, among other things, to automatically calculate the total
current from the current density vector. The analogy is valid for other fluxes.

CROSS SECTIONAL AREA

For 1D components, the Cross sectional area field (default value: 1 m2) defines a
parameter for the area of the geometry perpendicular to the 1D component. The value
of this parameter is used, among other things, to automatically calculate the total
current from the current density vector. The analogy is valid for other fluxes.

TRANSPORT MECHANISMS
Diffusion is always included. By default, the Convection and Migration in electric field
check boxes are not selected under Additional transport mechanisms.

• Selecting the Convection check box enables the addition of the Inflow and Outflow
boundary nodes.
• Selecting the Migration in electric field check box activates the migration transport of
ionic species in the Transport Properties node. Since supporting electrolytes of high
conductivity are usually used in electroanalytical problems, migrative effects are
usually negligible.

The physics interface has one tailor-made study type, see Cyclic
Voltammetry in the COMSOL Multiphysics Reference Manual.

Cyclic Voltammetry at a Macroelectrode in 1D Application Library

path: Electrochemistry_Module/Tutorials/cyclic_voltammetry_1d

• Theory for the Electroanalysis Interface

• Domain, Boundary, and Pair Nodes for the Electroanalysis Interface

In the COMSOL Multiphysics Reference Manual see Table 2-3 for links
to common sections and Table 2-4 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

100 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Domain, Boundary, and Pair Nodes for the Electroanalysis Interface
The Electroanalysis Interface has these domain, boundary, and pair nodes available,
listed in alphabetical order, available from the Physics ribbon toolbar (Windows users),
Physics context menu (Mac or Linux users), or right-click to access the context menu
(all users).

In general, to add a node, go to the Physics toolbar, no matter what

operating system you are using. Subnodes are available by clicking the
parent node and selecting it from the Attributes menu.

A boundary pair occurs when the solutions on two separate surfaces

within a simulation are related (such as when two components in an
assembly are touching)

These nodes are described in this section:

• Transport Properties • Electrode Reaction

• Electrode Surface in the • Initial Values
Electroanalysis Interface

THE ELECTROANALYSIS INTERFACE | 101

 These nodes are shared with and described for the Transport of Diluted Species
interface (listed in alphabetical order):

• Concentration • Open Boundary

• Electrode Surface Coupling • Outflow
• Equilibrium Reaction • Periodic Condition
• Flux • Porous Electrode Coupling
• Flux Discontinuity • Reaction Coefficients
• Double Layer Capacitance1 • Reactions
2
• Inflow • Symmetry
• No Flux • Thin Diffusion Barrier
1 This is documented for the Current Distribution interfaces

2
This is available when the Convection check box is selected on the physics interface
Settings window.

Some of the above nodes require that you click the Show button ( ) and
select Advanced Physics Options to enable the option in the context menu.
This requirement is for Flux Discontinuity, Periodic Condition, Thin Diffusion
Barrier, Electrode-Electrolyte Interface Coupling, Porous Electrode Coupling,
and Reaction Coefficients.

In the COMSOL Multiphysics Reference Manual see Table 2-3 for links
to common sections and Table 2-4 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Transport Properties
This node defines the transport properties of the electrolyte. What settings are
available is dependent on the transport mechanisms that have been chosen in the
Electroanalysis interface top node (any combination of convection, migration, and
diffusion), and includes only the input fields required by the activated transport
mechanisms.

102 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

MODEL INPUTS
The Temperature is User defined by default. If a Heat Transfer interface is included in
the model, alternatively select the temperature for that interface. For example, if a Heat
Transfer in Fluids interface is included in the model, the Temperature (ht) option is
available.

CONVECTION
This section is available when the Convection check box is selected on the interface top
node. The Velocity field u (SI unit: m/s) of the solvent is specified as a feature input.
The default is User defined, but if a Fluid Flow interface is included in the model, you
may select the velocity field for that physics interface. For example, if a Laminar Flow
interface is included in the model, the Velocity field (spf) option is available from the
list.

DIFFUSION
Enter the Diffusion coefficient Dc manually, or use a value from the Materials node. The
default Diffusion coefficient value is 10−9 m2/s, which is a typical order of magnitude
for a species diluted in a liquid aqueous solution.

MIGRATION IN ELECTRIC FIELD

You may include migration by selecting the Migration in electric field check box on the
Electroanalysis top node.

Choose the source for where the Electrolyte potential φ l (SI unit: V). Note that the
migration term in the transport equation is based on the gradient of the electrolyte
potential. If there is no spatial variation in φ l , the migration term will be zero.

By default the Mobility (s·mol/kg) is set to be calculated based on the species diffusivity
and the temperature using the Nernst-Einstein relation.

Only species with a non-negative Charge number zc (dimensionless, but requires a plus
or minus sign) will be affected by the migrative transport.

Initial Values
The Initial Values node adds the initial values for the concentration of each species to
be specified. These serve as an initial guess for a stationary solver or as an initial
condition for a transient simulation.

Add multiple Initial Values nodes with different domain selections to define different
initial values in different domains.

THE ELECTROANALYSIS INTERFACE | 103

 Setting all the Concentration (SI unit: mol/m3) initial values to 0 may lead solver
convergence problems, for instance in models using concentration dependent kinetics
in an Electrode Reaction node. Using small positive values instead of 0 may mitigate
such issues.

Electrode Surface in the Electroanalysis Interface

The Electrode Surface node defines an electrode surface located on an external
boundary to a Transport Properties (electrolyte) domain. The node will set up a flux
boundary condition, based on electrode reaction current densities and stoichiometric
coefficients according to Faraday’s law of electrolysis.

By default, an Electrode Reaction subnode is added to the feature and an arbitrary

number of these subnodes can be added, which contribute to the total flux over the
boundary. You may also add a Double Layer Capacitance subnode.

The overpotential used by the Electrode Reaction subnode is based on the electric
potential of the Electrode Surface, the electrolyte potential and the individual
equilibrium potentials of the Electrode Reaction subnodes.

Use the Boundary Condition section to control the electric potential. The electrolyte
potential is set to 0 by default. To use another value, enable Migration Electric Field on
the Electroanalysis top node, and set the value on the Transport Properties node. The
Film Resistance section can also contribute to the overpotentials.

FILM RESISTANCE
Use a film resistance if you want to include an additional potential drop due to an
ohmic resistance at the interface between the electrode and the electrolyte, for instance
due to build-up of insulating deposits.

Specify either a Surface resistance Rfilm (SI unit: Ω·m2) directly or choose the Thickness
and conductivity option to calculate the surface resistivity based on a depositing film
thickness.

HARMONIC PERTURBATION
Use this section in conjunction with AC Impedance study types to control the
perturbation amplitude in the frequency domain.

The perturbation parameter is either Electric potential, Electrode potential, Total current
or Average current density, based on the Boundary condition selected in the next section.

The frequency spectrum is specified in the study node.

104 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

This section is not available if Counter electrode is selected as the Boundary condition.

BOUNDARY CONDITION
This section specifies the potential in the electrode phase of the electrolyte-electrode
interface. The electrode potential is used (via the overpotential) by the Electrode
Reaction subnodes.

Electric potential, Electrode potential and Cyclic voltammetry will set the potential value
directly, whereas Total current, Average current density, and External short all add an
extra global degree of freedom for the potential in the electrode phase, set to comply
with the chosen condition.

The Counter electrode option will set a potential to ensure an overall charge balance of
the cell so that the integral of all electrode reaction currents of all electrode surface
node sums up to zero.

When using the Total current option in 1D or 2D, the boundary area is based either
on the Cross sectional area (1D), or the Out-of-Plane thickness (2D) properties, set on
the physics interface top node.

The Cyclic voltammetry setting varies the electric potential linearly in time as follows
when used in conjunction with a Cyclic Voltammetry study step:

End potential
Cycle 1 Cycle 2

Vertex 1

Vertex 2

Start potential

Figure 3-1: Electric potential vs time generated by the cyclic voltammogram boundary
condition. The linear sweep rate is 100 mV/s, the number of cycles is 2. Potentials levels are
also shown.

THE ELECTROANALYSIS INTERFACE | 105

 More advanced waveforms can be obtained using the Electric potential option with a
parameter setting based on Functions found in the Definitions menu.

ADVANCED SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.

If Cyclic voltammetry is selected as the Boundary condition, the Smoothing of cyclic

voltammetry wave functions check box is selected by default and the Smoothing factor
defaults to 1·10-3. When enabled, smoothing is applied on the triangular wave around
the vertex potentials. The smoothing zone corresponds to the product of the
smoothing factor with half the duration of one period of the triangular wave. .

• Cyclic Voltammetry and Waveform in the COMSOL Multiphysics

Reference Manual
• Theory for the Coupling of Mass Transport to Electrochemical
Reactions
• Counter Electrodes and Overall Charge Balance

Cyclic Voltammetry at a Macroelectrode in 1D Application Library

path: Electrochemistry_Module/Tutorials/cyclic_voltammetry_1d

Electrode Reaction
The Electrode Reaction subnode defines the electrode kinetics for the charge transfer
reaction that occurs between the electrolyte and the electrode on the surface of a
non-porous electrode. A default node is added where the electrode kinetics can be set
up for the charge transfer reaction. The Electrode Reactions subnode is added by default
to the Electrode Surface in the Electroanalysis Interface. You can also add it from the
context menu (right-click the parent node) or from the Physics toolbar, Attributes
menu.

ELECTRODE KINETICS
Except for the Electroanalytical Butler-Volmer settings described below, see the
Electrode Reaction node for information about the other settings.

The Electroanalytical Butler-Volmer is a concentration dependent kinetics expression

based on a Heterogeneous rate constant k0 (SI unit: m/s), the Cathodic transfer

106 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

coefficient ac (dimensionless) and the reaction coefficients settings on the
Stoichiometric Coefficients section by which cred and cox are determined.

The Electroanalytical Butler–Volmer Equation

THE ELECTROANALYSIS INTERFACE | 107

 Theory for the Current Distribution
Interfaces
In this section:

• The Nernst-Planck Equations

• Domain Equations for Primary and Secondary Current Distributions
• Electrochemical Reactions and the Difference Between a Primary and a Secondary
Current Distribution
• Domain Equations for Tertiary Current Distributions Using the Nernst-Planck
Equations and Electroneutrality
• Mass Fluxes and Sources Due to Electrochemical Reactions
• Film Resistance
• Electrode Kinetics Expressions
• Theory for Specific Current Distribution Feature Nodes

This theory is also relevant to the Current Distribution on Edges, BEM

interface. However, due to the use of BEM, current source terms in the
electrolyte, and porous electrodes, cannot be used in this interface.

The Nernst-Planck Equations

The general mass balance for the diluted species in an electrolyte is described by the
following equations for each species i:

∂c i
+ ∇ ⋅ N i = R i, tot
∂t

where Ni is the total flux of species i (SI unit: mol/(m2·s)). The flux in an electrolyte
is described by the Nernst-Planck equations and accounts for the flux of charged solute
species (ions) by diffusion, migration, and convection; these are respectively the first,
second, and third term on right side in the equation below.

N i = – D i ∇c i – z i u m, i Fc i ∇φ l + c i u = J i + c i u

108 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

where

• ci represents the concentration of the ion i (SI unit: mol/m3),

• zi its valence,
• Di the diffusion coefficient (SI unit: m2/s),
• um,i its mobility (SI unit: s·mol/kg),
• F denotes the Faraday constant (SI unit: C/mol),
• φ i the electrolyte potential,
• u is, the velocity vector (SI unit: m/s), and
• Ji denotes the molar flux relative to the convective transport.

J i = – D i ∇c i – z i u m, i Fc i ∇φ l (3-2)

The net current density can be described using the sum of all species fluxes:

il = F  zi Ni
where il denotes the current density vector (SI unit: A/m2) in the electrolyte.

Domain Equations for Primary and Secondary Current

Distributions
Assuming electroneutrality (which cancels out the convection term) and negligible
concentration gradients of the current-carrying ion (which cancels out the diffusion
term), the following expression is left for the current density vector in an electrolyte:

 zi um, i ci ∇φl .
2 2
il = –F

Further, assuming approximately constant composition of charge carriers, we can

define a constant electrolyte conductivity as:

 zi um, i ci
2 2
σl = F

the current density in the electrolyte can be written as

i l = – σ l ∇φ l

This equation takes the same form as Ohm’s law; in an electrolyte, charge transport is
ohmic, subject to the above assumptions.

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 109

 Conservation of charge yields the domain equation usually used for the electrolyte in
the Primary and Secondary Current Distribution interfaces:

∇ ⋅ il= 0

In a pore electrolyte, the homogenization used in porous electrode

theory introduces a source or sink term in the pore electrolyte current
balances due to the charge transfer reactions at the electrode-electrolyte
interface within the porous material. In such cases, a source term, Ql, is
introduced on the right-hand side of the equation above.

The Primary and Secondary Current Distribution interfaces define two dependent
variables: one for the potential in the electrolyte and one for the electric potential in
the electrode. The conduction of current in the electrolyte is assumed to take place
through transport of ions as described above, while electrons conduct the current in
the electrode.

Since Ohm’s law is also used for current conduction in the solid electrode phase, the
general equation in these interfaces is according to the following:

∇ ⋅ ik = Qk

with

i k = – σ k ∇φ k

where Qk denotes a general source term, k denotes an index that is l for the electrolyte
or s for the electrode, σk denotes the conductivity (SI unit: S/m) and φ k the potential
(SI unit: V).

Electrochemical Reactions and the Difference Between a Primary and

a Secondary Current Distribution
Both the primary and secondary current distribution models assume an electrolyte that
conducts current according to Ohm's law, with a constant conductivity. The difference
between a primary and a secondary current distribution lies in the description of the
electrochemical charge transfer reaction at the interface between an electrolyte and
an electrode. The charge transfer reactions can be defined as boundary conditions, or
as sources or sinks in a domain for the case of porous electrodes.

110 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

The rate of the electrochemical reactions can be described by relating the reaction rate
to the activation overpotential. For an electrode reaction, with index m, the activation
overpotential, denoted ηm, is the following:

η m = φ s – φ l – E eq, m

where Eeq,m denotes the equilibrium potential (also known as a reduction potential)
for reaction m.

In the Primary Current Distribution interface, the electrochemical reactions are

assumed to be fast enough that their kinetics have negligible influence on the cell
voltage. Consequently, the activation overpotential, ηm, in this physics interface is
equal to zero, and the difference in potential between the electrode and the electrolyte
is always equal to the equilibrium potential, E eq, m. This condition is implemented as
the following constraint on boundaries between electrodes and electrolyte domains:

φ l = φ s – E eq, m

A good modeling practice is to estimate the influence of finite reaction

kinetics on the cell voltage and to compare the associated activation losses
to the ohmic losses in a cell to check the validity of the primary current
distribution assumption.

In the Secondary Current Distribution interface, the electrochemical reactions are

described as a function of the overpotential. The physics interface uses several relations
for the charge transfer current density and the overpotential, such as Butler-Volmer
and Tafel expressions. The most general expression is of Butler-Volmer type:

α a Fη – α c Fη
i loc,m = i 0  exp  --------------- – exp  ----------------- 
  RT   RT  

where iloc,m denotes the local charge transfer current density for reaction m, i 0 the
exchange current density, αa the anodic transfer coefficient, αc the cathodic charge
transfer coefficient, F Faraday’s constant, and R the universal gas constant.

It is possible to expand the expression above to include the dependence

of kinetics on concentration.

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 111

 The sum of all electrode reaction currents is implemented as a current density
condition on the boundary between an electrode and an electrolyte domain according
to:

il ⋅ n =  iloc, m
m

is ⋅ n = –  iloc, m
m

Both the Primary Current Distribution and Secondary Current Density Distribution
interfaces allow for a domain definition for porous electrodes. For the Primary Current
Distribution interface, the same constraint as above is applied.

In porous electrodes for the Secondary Current Distribution interface, the sum of all
reaction currents appears as a source in the domain equations:

∇ ⋅ il =  Av, m iloc, m
m

∇ ⋅ is = –  Av, m iloc, m
m

where Av,m is the surface area.

The only reason to add Porous Electrode descriptions to the Primary

Current Distribution interface is to be able to expand a model to include
charge transfer resistance.

Domain Equations for Tertiary Current Distributions Using the

Nernst-Planck Equations and Electroneutrality
The domain equations can be derived by starting with The Nernst-Planck Equations.
The material balance equation for the species i in the electrolyte is given by the
continuity equation, with a flux given by the Nernst-Planck equation:

∂c i
+ ∇ ⋅ ( J i + c i u ) = R i, tot
∂t

112 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

where

• ci denotes the concentration of species i (SI unit: mol/ m3),

• u is, the velocity vector (SI unit: m/s), and
• Ji denotes the molar flux relative to the convective transport(see Equation 3-2)

The current balance includes the sum of the flux of all charged species, which yields
the current density in the electrolyte:

n n

il = F  z i ( – D i ∇c i – z i u m , i F c i ∇φ l )  zi Ji
= F
i=1 i=1

The concentration gradients are not assumed to be negligible here, and

so the contribution of ion diffusion to overall current density can be
nonzero. (Compare with the Domain Equations for Primary and
Secondary Current Distributions.)

In the equations above, il denotes the current density vector in the electrolyte. The
current balance in the electrolyte then becomes:

∇ ⋅ il = Ql

where Ql can here be any source or sink. (Ql is typically nonzero for porous
electrodes). The current balance and the material balances give one equation per
unknown species concentration. However, there is still one more unknown, the
electrolyte potential, which requires an additional equation. This equation is the
electroneutrality condition, which follows from dimensional analysis of Gauss’s law. In
a typical electrolyte solution, it is accurate over lengths greater than a few nanometers:

 zi ci = 0

These formulations are also valid for the pore electrolyte in porous electrodes, except
for the transport properties that have to be corrected for porosity and tortuosity. In
such cases, the source or sink, Ql, denotes the charge transfer reactions in the porous
electrode and/or the non-Faradaic source or sink due to double layer charge and
discharge.

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 113

 The charge transfer reaction can be parameterized by arbitrary functions of the
concentrations of the species in the redox couple and the local electric and electrolyte
potentials. The most common way to describe the reaction kinetics is to use a
Butler-Volmer expression for the charge transfer current density, iloc (SI unit: A/m2),
which in this case can contain concentration dependencies:

ci γ i, a α a Fη ci γ i, c – α c Fη
i loc = i 0  ∏  ------------
- exp  --------------- – ∏  ------------
- exp  ----------------- 
c i, ref RT c i, ref RT

where i0 denotes the exchange current density (SI unit: A/m2), αa the anodic charge
transfer coefficient (dimensionless), αc the cathodic charge transfer coefficient
(dimensionless), γi,a the anodic reaction order for species i (dimensionless), and γi,c is
the cathodic reaction order for species i (dimensionless). The overpotential, η, is
defined as in preceding sections, according to the following equation:

η = φ s – φ l – E eq

In the current balance in a porous electrode, the local current density multiplied by the
specific surface area of an electrode gives a contribution to the source or sink, Ql, due
to electrochemical reactions.

Mass Fluxes and Sources Due to Electrochemical Reactions

When relating the species fluxes at an electrode surface to the electrical currents, the
general electrochemical reaction formula:

 νox Sox + ne  νred Sred

-
⇔
ox red

is used to define the stoichiometric coefficients, νi, with νi being positive (νred) for
products and negative (νox) for the reactants in a reduction reaction. The number of
participating electrons, n, is always positive.

The molar species fluxes, Ni (SI unit: mol/(m2·s)), perpendicular to an

electrode-electrolyte interface are calculated by summing all the flux contributions
from the electrode reactions of index m, according to Faraday’s laws:

ν i, m i m
Ni =  -----------------
nm F
-
m

114 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

where im is the local current density (SI unit: A/m2) of the electrochemical reaction,
nm the number of participating electrons and F (SI unit: C/mol) is the Faraday
constant.

The molar species flux, Ni, is obtained from the normal component of the molar
species flux vector over the electrode-electrolyte interface:

Ni = Ni ⋅ n

where n is the normal vector of the boundary pointing into the domain.

For a porous electrode, the electrochemical reactions result in species source terms
calculated from:

ν i, m i m
R i, molar = –  av, m -----------------
nm F
-
m

2 3
where av,m (SI unit: m /m ) is the specific surface area.

Stochiometric Coefficients for Double Layer Capacitive Charging

A negative capacitive current corresponds to the accumulation of negative charge on
the electrode surface, and a corresponding counterbalanced positive charge
accumulating in the double layer. This can be understood in terms of conservation of
current: cathodic capacitive current at the electrode corresponds to the overall
injection of negative charge (from the double layer) into the electrolyte, just as a
cathodic Faradaic current would add negative charge to the electrolyte through
electron transfer.

Consider an overall reaction as:

- + -
2e (electrical circuit) + A (solution) + X (double layer)

- + -
2e (electrode surface) + A (double layer) + X (solution)

This corresponds to a negative charge of 2F being moved from double layer to

solution. Following the convention that the reaction is written in the order of cathodic
current (as above), then with respect to the free solution species, the cation is a reactant
(negative stoichiometry) and the anion is a product (positive stoichiometry). This
suggests νA = −1, νX = +1, and n = 2 for an ideal double layer where both anion and
cation have similar contributions to the double layer charge.

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 115

 Film Resistance
If a resistive film forms on the interface between an electrode and an electrolyte, this
results in additional potential losses. To model a film resistance, an extra dependent
variable for the potential drop over the film, Δ φ s,film, is introduced. The governing
equation is:

Δφ s, film = i tot R film

Where Rfilm (SI unit: ohm·m2) is a generalized film resistance and itot the sum of all
currents over the interface. The activation overpotentials, ηm, for all occurring
electrode reactions on the electrode with the film receive an extra potential
contribution due to the film resistance according to:

η m = φ s – Δφ s, film – φ l – E 0, m

If the thickness and conductivity of the film are known, the resistance can be written as:

s 0 + Δs
R film = ------------------
σ film

where s0 is the reference/initial film thickness, Δs the electrode thickness change, and
σfilm the conductivity (S/m) of the film.

Electrode Kinetics Expressions

A number of different analytical expressions for iloc,m are available. In the following
the index m is dropped. All parameters are understood to refer to a specific reaction.

The Equilibrium Potential and the Overpotential

The rate of the electrochemical reactions can be described by relating the reaction rate
to the activation overpotential (or reduction potential). For an electrode reaction, the
activation overpotential, denoted η, is the following:

η = φ s – φ l – E eq

where Eeq denotes the equilibrium potential.

Butler-Volmer
The most general expression is of Butler-Volmer type:

116 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

 α a Fη – α c Fη
i loc = i 0  exp  --------------- – exp  ----------------- 
  RT   RT  

where αc denotes the cathodic charge transfer coefficient, αa the anodic charge transfer
coefficient.

Linearized Butler-Volmer
The charge transfer reaction can be expressed by a linearized Butler-Volmer expression,
which can be used for small overpotentials (η << RT/F) and is usually referred to as
the low-field approximation. This approximation gives the following linearized
equation:

( α a + α c )F
i loc = i 0  ---------------------------- η
 RT 

where αc denotes the cathodic charge transfer coefficient, αa the anodic charge transfer
coefficient, i0 the exchange current density, and η the overpotential.

Anodic and Cathodic Tafel Equations

By assuming either high anodic or cathodic overpotentials for a given current (that is,
slow kinetics or low i0), one of the terms in the original Butler-Volmer potentials can
be neglected.

The anodic Tafel equation is implemented as follows:

η ⁄ Aa
i loc = i 0 ⋅ 10

where Aa (SI unit: V) is the so-called Tafel slope. The cathodic Tafel expression is
according to:

η ⁄ Ac
i loc = – i 0 ⋅ 10

to account for the negative sign of cathodic charge transfer reactions. Ac is also
required to be negative.

Concentration Dependent Kinetics

The following expression describes a charge transfer reaction according to the full
Butler-Volmer equation, where the anodic and cathodic terms of the current density
expression depend on the local concentrations of the electroactive species at the
electrode surface:

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 117

 α a Fη – α c Fη
i loc = i 0  C R exp  --------------- – C O exp  ----------------- 
  RT   RT  

where CR and CO are dimensionless expressions, describing the dependence on the

reduced and oxidized species in the reaction.

Exchange Current Density and Rate Constants

The exchange current density typically depends on the local concentrations of the
reacting species. For instance, for a one electron redox couple, defining CO = co / cref,
CR = cr / cref, and i0=k0Fcref, the above expression can be rewritten as

α a Fη – α c Fη
i loc = k 0 F  c r exp  --------------- – c o exp  ----------------- 
  RT   RT  

where k0 (m/s) is the heterogeneous rate constant.

Limiting Current Density

The steady-state rate of electrode reactions never exceeds the rate at which reactants
and products can be transported to and from the electrode surface. When explicitly
including mass transport in a model, this dependence is typically described by a
concentration dependent kinetics expression as described above.

By the assumption of a Nernst diffusion layer at the electrode surface, and a first order
dependence between the charge transfer current and the local concentration of a
reacting species, the following kinetics expression can be derived:

i expr
i loc = -------------------------
i expr
1 + ----------
i lim

where iexpr (A/m2) is the current density expression in the absence of mass transport
limitations for the species, and ilim (A/m2) is the limiting current density that
corresponds to the maximum transport rate of the species. The derivation of this
expression assumes either a strictly anodic or an cathodic reaction.

Theory for Specific Current Distribution Feature Nodes

ELECTROLYTE THEORY
The Electrolyte node defines a current balance in the electrolyte. The domain equation
is:

118 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

 ∇ ⋅ il = 0

where il denotes the current density vector. In free electrolyte, there is no source or
sink of charge.

The definition of the current density vector depends on the equation formulation of
the electrolyte charge transport, as discussed above in Domain Equations for Primary
and Secondary Current Distributions and Domain Equations for Tertiary Current
Distributions Using the Nernst-Planck Equations and Electroneutrality.

• For the Primary and Secondary Current Distribution interfaces, see

Electrolyte.
• For the Tertiary Current Distribution, Nernst-Planck interface, see
Electrolyte.

POROUS ELECTRODE THEORY

A porous electrode is a mixed material with one electrode phase and one electrolyte
phase. (A special case of a porous electrode is the gas diffusion electrode, as found in
a fuel cell. These contain a gas pore phase which is inert to charge transfer.) To model
a porous electrode we define two separate current balances according to the following
equations:

∇ ⋅ i l = Q l and ∇ ⋅ i s = Q s

In these equations, il denotes the current density vector in the electrolyte, as discussed
above in Domain Equations for Primary and Secondary Current Distributions and
Domain Equations for Tertiary Current Distributions Using the Nernst-Planck
Equations and Electroneutrality.

In addition to the current balances, it is necessary to also formulate mass balance

equations for the species in the electrolyte phase for the tertiary case.

It is also common to used corrected conductivities and diffusion parameter values in a

porous electrode to account for the lowered volume fraction of the conducting phase,
and the longer transport distance due to the tortuosity of the pores.

The current balances in the pore electrolyte and in the electrode matrix contain sources
and sinks according to the charge transfer reactions that take place in the electrode
catalyst. For example, if only one charge transfer reaction takes place in the porous

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 119

 electrode and the rate of this reaction is described by the Butler-Volmer equation, the
domain equations are the following:

α a Fη – α c Fη
∇ ⋅ i l = A v ⋅  i 0  exp  --------------- – exp  -----------------  
   RT   RT   
α a Fη – α c Fη
∇ ⋅ i s = – A v ⋅  i 0  exp  --------------- – exp  -----------------  
   RT   RT   

where Av denotes the specific surface area (dimension L2/L3), and η the overpotential
according to

η = φ s – φ l – E eq

and Eeq denotes the equilibrium potential for the charge transfer reaction.

If the porous electrode is a cathode, then the charge transfer reaction is a source for
the current balance in the electrode, because it receives current from the pore
electrolyte. The charge transfer reaction is then a sink for the current balance in the
pore electrolyte, because the current is transferred from the pore electrolyte to the
electrode in a cathodic reaction.

The corresponding sources and sinks in the current balances that are due to the charge
transfer reactions are also coupled to the material balances for the charged species. This
means that the exemplar Butler-Volmer expression above is also included in the
material balances as a reaction term, Ri, by using Faraday’s laws for each of the species
that take part in charge transfer reactions.

• For the Primary and Secondary Current Distribution interfaces, see

Porous Electrode.
• For the Tertiary Current Distribution, Nernst-Planck interface, see
Porous Electrode.

ELECTRODE REACTIONS THEORY

Charge transfer reactions occurring at an interface between an electrode and an
electrolyte domain gives rise to a normal current flux that equals the sum of all reaction
currents according to

120 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

 il ⋅ n =  iloc, m
m

is ⋅ n = –  iloc, m
m

where iloc,m (A/m2) is the Electrode Reaction current density of the charge transfer
electrode reaction of index m, il the current density vector in the electrolyte and is the
current density vector in the electrode.

POROUS ELECTRODE REACTIONS THEORY

For a porous electrode, the electrode reaction current densities are multiplied by the
surface area to yield a source or sink in the current balance domain equation according
to:

∇ ⋅ il =  Av iloc, m
m

∇ ⋅ is = –  Av iloc, m
m

where Av is the specific surface area of the electrocatalyst.

Porous Electrode Reaction

ELECTRODE THEORY
Electron conduction in an Electrode is modeled using Ohm’s law. The domain
equation is the following:

∇ ⋅ is = 0

where is denotes the current density vector according to:

i s = – σ s ∇φ s

and where σs denotes the electrical conductivity and φ s the electrolyte potential.

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 121

 ELECTROLYTE CURRENT DENSITY THEORY
An applied current density can be defined as its component perpendicular to the
boundary according to:

i l ⋅ n = i n, l

The current density can also be defined including all its components:

i l = i l, bnd

where il, bnd is a given expression for the current density vector.

Electrolyte Current Density

ELECTROLYTE CURRENT THEORY

The Electrode Current boundary condition sets the total current at a given position in
the electrolyte without imposing a current density distribution. The conditions yields
a constant electrolyte potential, along the given boundary, that satisfies the total value
of the current. The boundary condition is a good choice in the middle of a cell with
planar electrodes, where the isopotential level can be a plane (or close to a plane in 3D,
or line in 2D) but where the current density distribution is unknown.

The feature adds one unknown variable, the electrolyte potential, φ l, bnd, along the
boundary. It then adds one additional equation for the total current, which is an
integral over the boundary:

 i l ⋅ n ds = I n, l
∂Ω

The average current density condition imposes the same equation but multiplies the
current density by the area of the boundary to obtain the value of the total current In, l.

ELECTRODE CURRENT THEORY

The Electrode Current adds one unknown variable, the electric potential, φ s, bnd,
along the boundary. It then adds one additional equation for the total current, which
is an integral over the boundary:

 i s ⋅ n ds = I n, s
∂Ω

122 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

where

i s = – σ s ∇φ s

and σs denotes the electrode conductivity and φ s the electric potential. The average
current density condition imposes the same equation but multiplies the current density
by the area of the boundary to obtain the value of the total current, In,s.

SYMMETRY THEORY
The Symmetry boundary condition, in the Primary Current Distribution and
Secondary Current Distribution interfaces is identical to the Insulation condition and
is expressed according to the equation below.

ik ⋅ n = 0

where ik denotes the current density vector and k = l, s is an index for the electrolyte
and electrode, respectively.

The Symmetry boundary condition for the Tertiary Current Distribution,

Nernst-Planck interface imposes a no-flux condition for the molar flux of species at a
boundary. The condition is expressed as follows:

Ji ⋅ n = 0

ELECTRODE CURRENT DENSITY THEORY

An applied Electrode Current Density can be defined as its component perpendicular
to the boundary according to:

i s ⋅ n = i n, s

where

i s = – σ s ∇φ s

and σs denotes the electrode conductivity and φ s the electric potential.

The current density can also be defined including all its components:

i s = i s, bnd

where is, bnd is a given expression for the current density vector.

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 123

 ELECTRODE POWER THEORY
The Electrode Power boundary condition is used to specify either the total electrode
power or the average electrode power density drawn from or inserted into an
electrochemical cell at an electrode boundary.

For a total power condition, the boundary electric potential of an electrode is set to a
potential φ s, bnd, defined by the condition for the total power on the boundary ∂Ω
according to:

φ s = φ s, bnd on ∂Ω

 ( φs, bnd – φs, ground ) ( is ⋅ n ) dS = P total

∂Ω

where φ s, ground is the ground potential of the cell, and Ptotal (W) is the power to be
drawn.

For an average power condition, Ptotal is calculated by:

P total = P avg A

where Pavg is the average power density on the boundary, and A is the boundary area.

For a galvanic cell, such as a battery during discharge or a fuel cell, there
is a maximum power level, beyond which a further current increase causes
a lowered output power due to increasing voltage losses. A result of this
is that there can be two existing solutions for the same power setting. In
these cases the choice of initial values determines the final solution.

Electrode Power

ION EXCHANGE MEMBRANE THEORY

Ion-exchange membranes typically contain a polymer matrix with a number of fixed
ionic groups.

Since these charges are fixed, there is no need to explicitly model the transport of these
charges, but when calculating the sum of charges, used in the Nernst-Planck (with
electroneutrality) or the Nernst-Planck-Poisson set of equations, one need to add this
fixed space charge.

124 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

For Nernst Planck with electroneutrality, the electroneutrality condition reads

ρ fix + F  zi ci = 0

For the Nernst-Planck-Poisson case, the total space charge density becomes

ρ v = ρ fix + F  zi ci
ION EXCHANGE MEMBRANE BOUNDARY THEORY
The electrochemical potential μi of a charged species of index i is

μ i = RT ln a i + φ l z i F

where T(K) is the temperature, R (mol/(J K)) the molar gas constant, ai is the species
activity, φ l is the electrolyte potential, zi the species charge and F(C/mol) is Faraday's
constant.

At equilibrium the electrochemical potentials on each side of the free electrolyte -

ion-exchange membrane interface are equal.

Setting the species activity to equal the concentration and denoting the liquid
electrolyte phase and a ion-exchange membrane phases as 1 and 2, respectively, the
Donnan potential, Δφ (V), describes the relation between the concentration of a
species, ci (mol/m3), at each side of the boundary and the electrolyte potentials:

c i, 1
Δφ l = φ l, 1 – φ l, 2 = – -------- ln  ---------
RT
z i F  c i, 2

which may be rearranged to

z i F ( φ l, 1 – φ l, 2 )
c i, 2 = c i, 2 exp  – ---------------------------------------
 RT 

The molar flux of each species in the liquid electrolyte is continuous over the
membrane-liquid interface

n ⋅ J i, 1 = n ⋅ J i, 2

Since the total current density is the sum of all species fluxes, times the individual
species charges, the current densities Il in the normal direction n of the
membrane-liquid interface boundary is also continuous:

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 125

 n ⋅ I l, 1 = n ⋅ I l, 2

126 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Theory for Electrochemical Heat
Sources
Irreversible voltage losses in an electrochemical cell can occur due to the following
phenomena:

• Charge transport in the electrolyte (Joule heating)

• Charge transport in the solid conductor materials (Joule heating)
• Activation overpotentials in the electrode reactions
• Heat of mixing

In addition, reversible heat sources and sinks can appear due to the entropy changes in
the electrode reactions.

Most Electrochemistry interfaces define and announce heat source variables that for
instance can be used by the General Source and the Boundary Heat source nodes in
the Heat Transfer interfaces.

An alternative way to couple an electrochemical interface to a heat transfer interface is

by the use of the Multiphysics nodes that become available in the model builder tree if
there is both a Heat Transfer interface and an Electrochemistry interface available in
the same component.

The Electrochemical Heating multiphysics node defines a domain heat source in the
heat transfer interface, based on the sum of irreversible (Joule heating and activation
losses) and reversible heat in the electrochemistry interface.

You can also use the heat source variables defined by the electrochemistry interfaces
when setting up manual heat couplings between different components in a model. For
instance if you are using a 1D electrochemical cell model to calculate an average heat
source in a 3D heat transfer model. The names of the heat source variables are xxx.Qh
(domain, Joule heating and porous electrode reactions) and xxx.Qbfc (boundary,
electrode surface reactions), where xxx is the electrochemistry interface identifier.

• Electrochemistry Interfaces
• Multiphysics Coupling Nodes

THEORY FOR ELECTROCHEMICAL HEAT SOURCES | 127

 Joule Heating Due to Charge Transport
The charge transport in the solid conductor material and electrolyte create joule
heating source terms according to

Q JH = – ( i s ⋅ ∇φ s + i l ⋅ ∇φ l ) (3-3)

Heating Due to Electrochemical Reactions

For an electrochemical reaction process one can write the total heat balance as:

• Heat generated = Total reaction enthalpy – Electrical energy leaving the system
Using Faraday’s law for an electrode reaction, m, at the interface between the electron
and ion conducting phase this corresponds to

ΔH m ΔG m
Q m =  ------------- –  ------------- – η m, tot  i m (3-4)
 nm F  nm F 

where ΔHm is the enthalpy change of the reaction, and ΔGm is the Gibbs free energy
of the reaction, ΔGm, defined as

ΔG m = ΔH m – TΔS m

where ΔSm is the net entropy change. Equation 3-4 may now be rearranged into

TΔS m
Q m =  η m, tot + ---------------- i m (3-5)
 nm F 

where the first term represents the irreversible activation losses, and the second term
is the reversible heat change due to the net change of entropy in the conversion
process.

In Equation 3-4 we have used the total overpotential, ηm,tot,(including potential

effects from film resistances and similar), defined as

η m, tot = φ s – φ l – E eq, m

The equilibrium potential is related to ΔGm in the following way:

ΔG m
E eq, m = – -------------
nm F

128 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

By the relation between the temperature derivative of the equilibrium potential and the
entropy:

∂E eq, m ΔS m
------------------
- = -----------
-
∂T nm F

the local heat source due to the electrochemical conversion process becomes

∂E eq, m
Q m =  η m, tot + T ------------------- i m
∂T

Alternatively, by defining the thermoneutral voltage of the reaction as

ΔH m
E therm, m = – -------------
nm F

one may also define the heat source as

Q m = ( η m, tot + ( E eq, m – E therm, m ) )i m

The total heat source due to the electrochemical reactions, QEC, for an electrode
surface is the sum of all individual heat sources of the electrode reactions according to

Q EC =  Qm
m

For a porous electrode joule heating and electrochemical sources are summed up for a
total heat source in the domain according to

Q TOT, p =  av, m Qm + QJH

m

Heating Due to Heat of Mixing

If the enthalpy varies with the local concentration of the reacting species of the
reaction, there are also heat of mixing sources associated with the concentration
gradients and resulting molecular flux of the reacting species from the bulk to the
surface that have to been to included for a correct thermal balance of the cell. The heat
of mixing effects are typically small (zero for ideal gases) and are generally not included
in the Electrochemistry interfaces.

THEORY FOR ELECTROCHEMICAL HEAT SOURCES | 129

 Theory for the Electrode, Shell
Interface
The Electrode, Shell Interfacedefines electrode current conduction on a thin shell on
a boundary. The electrolyte current distribution in the adjacent domain is typically
solved for by a separate physics interface.

In this section:

• Governing Equations
• Coupling to Other Physics Interfaces

Governing Equations
The Electrode, Shell interface solves for the electric potential φ s (SI unit: V) on a
boundary, using the following governing equation:

∇ T ⋅ ( si s ) = – i n (3-6)

where ∇T is the tangential gradient operator, s (SI unit: m) is the electrode layer
thickness, and in (SI unit: A/m2) are the sum of all currents flowing out from the
electrode (in the normal direction to the boundary). Furthermore, is (SI unit: A/m2)
is the tangential current density vector along the electrode boundary, defined as

i s = – ∇Tσ s φ s (3-7)

where σs is the electric conductivity (SI unit: S/m). The next section discusses
Coupling to Other Physics Interfaces.

Coupling to Other Physics Interfaces

ELECTRODE POTENTIAL IN OTHER PHYSICS INTERFACES

Typically the boundary electric potential in the Electrode Surface node is set to the
electric potential in the Electrode, Shell interface.

ELECTRODE REACTION CURRENTS

The sum of currents can be coupled to other electrochemistry interfaces, calculating
in as

130 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

 i n = i tot

where itot (SI unit: A/m2) is the sum of all electrode currents in the coupled
Electrochemistry interface.

ELECTRODE LAYER THICKNESS

The electrode thickness, s, can typically be coupled to an External Depositing
Electrode (External Corroding Electrode) node in the Electrodeposition, Moving
Mesh (Corrosion, Moving Mesh) interface, in that case s is calculated as

s = s 0 + Δs tot (3-8)

where s0 is the initial electrode layer thickness, and Δstot is the electrode thickness
change, calculated by the coupled Electrochemistry interface.

HEAT SOURCE
The electron conduction gives rise to a Joule heating source QH (SI unit: W/m2)
according to

Q H = – si s ⋅ ∇ t φ s

THEORY FOR THE ELECTRODE, SHELL INTERFACE | 131

 Theory for the Electroanalysis
Interface
The Electroanalysis Interface theory is described in this section:

• Electroanalytical Methods
• Supporting Electrolyte
• Domain Equations for the Electroanalysis Interface
• Electrodes in the Electroanalysis Interface
• The Electroanalytical Butler–Volmer Equation
• Counter Electrodes and Overall Charge Balance

Electroanalytical Methods
Electroanalysis is the science of quantitative electrochemical measurement of the
composition or properties of a chemical system. Common electroanalytical methods
include: (cyclic) voltammetry, (chrono)amperometry, potentiometry, coulometry, and
electrochemical impedance spectroscopy (EIS). These methods are experiments
performed either in a static electrolyte solution or in an electrolyte solution subject to
a forced fluid flow. The results sought in electroanalysis include:

• Measurement of the concentration of an analyte — for example, glucose, or a

gas-phase species that dissolves in the electrolyte solution. This technique is often
referred to as electrochemical sensing. The most common sensing method is by
recording the concentration-dependent current due to an analyte-specific reaction:
this is called amperometric sensing.
• Measurement of the kinetic and/or thermodynamic parameters describing an
electrochemical reaction on a given electrode surface.
• Measurement of the transport properties of an electroactive chemical species.
• Investigation of the mechanism of an electrochemical reaction and the further
reactivity of the electrochemically generated chemical species.

The Electroanalysis interface is designed for efficient simulation of electroanalytical

methods. Many of the features found in the physics interface are shared with the

132 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Current Distribution interfaces and Transport of Diluted Species interfaces, subject to
the simplifying assumption of zero electric field in the electrolyte solution.

• The Primary and Secondary Current Distribution Interfaces

• The Transport of Diluted Species Interface

Supporting Electrolyte
When performing electroanalytical experiments, it is conventional to add a large
quantity of inert salt to the solution — this artificially added salt is called supporting
electrolyte. The purpose of the supporting electrolyte is to increase the conductivity of
the solution, and hence to eliminate the electric field from the electrolyte.

A negligible electric field provides two advantages for electroanalysis:

• The voltage due to the resistance of the electrolyte when the cell draws current
(“ohmic drop”) is minimal. Therefore, the potential difference applied across the
electrochemical cell is localized at the electrode–electrolyte interfaces, and so the
activation overpotential perceived by the redox couple at this interface is almost
exactly proportional to the applied cell voltage. The kinetic behavior of the
electrochemical cell then has no explicit dependence on the magnitude of the drawn
current.
• The contribution of migration to the transport of charged chemical species is
negligible compared to the contribution of diffusion (and of convection, in a forced
flow). Therefore the transport properties of the system are linearized, and they do
not depend on the magnitude of the drawn current.

These properties greatly simplify the design and analysis of electroanalytical

experiments. Therefore, the use of a supporting electrolyte is very common in
electrochemical sensing and electroanalysis.

The amount of supporting electrolyte required for the assumption of zero

electric field to be sound is dependent on the system. Typically it becomes
valid when the concentration of inert salt exceeds the concentration of
analyte by a factor of 10–100, but this is not always the case.

Even for the conductivities of electrolyte solutions in the presence of excess supporting
electrolyte, the electric field is not negligible if significant current density is drawn.
Electroanalysis typically draws small currents because the purpose is measurement. In

THEORY FOR THE ELECTROANALYSIS INTERFACE | 133

 processes where an electrochemical reaction is driven—such as electrolysis,
electrodeposition, batteries, and fuel cells—current densities are typically much larger,
so that the desired extent of reaction is achieved in a reasonable time. Under these
conditions, significant electric fields are likely and one of the Current Distribution
interfaces should be used instead of the Electroanalysis interface.

Domain Equations for the Electroanalysis Interface

The Electroanalysis interface assumes that the electric field is zero, and so the
electrolyte potential is constant. Since you can arbitrarily choose to ground the
electrolyte potential at any point, set it to φ l = 0 .

This is equivalent to the assumption of infinite electrolyte conductivity. Therefore the

Electroanalysis interface does not solve for charge transfer within domains, because
current density is not meaningfully defined within the electrolyte.

The transport of chemical species in an electrolyte solution obeys the Nernst–Planck

equation for the flux of species i:

N i = – D i ∇c i – z i u m, i Fc i ∇φ l + c i u = J i + c i u

Here Ji denotes the molar flux relative to the convective transport.

At zero electric field, this reduces to:

N i = – D i ∇c i + c i u (3-9)

where the only contributions to the flux of a chemical species are from diffusion and
convection respectively. In the absence of convection (no fluid flow, u = 0), this is also
known as Fick’s first law of diffusion:

N i = J i = – D i ∇c i

A mass balance also applies to each chemical species:

∂c i
+ ∇ ⋅ N i = R i, tot (3-10)
∂t

The Electroanalysis interface solves Equation 3-9 and Equation 3-10 for the unknown
concentrations of each chemical species under analysis.

This combination is often written as a single equation for the unknown ci. For zero
convection, zero reaction, and a constant diffusion coefficient, the domain equation is:

134 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

 ∂c i 2
= Di ∇ ci (3-11)
∂t

Equation 3-11 is Fick’s second law of diffusion.

The Electroanalysis interface is not suitable to explicitly model the

transport of the supporting electrolyte, since the migration of the
supporting electrolyte is always its dominant mode of mass transport. For
a coupled model including the chemical species of all charge-carrying
species, use the Tertiary Current Distribution, Nernst–Planck interface.

With the Electroanalysis interface, you can include additional chemical

species and reactions that are not involved in the electrochemical reaction.

• Electrode Potentials and Reference Electrodes

• The Tertiary Current Distribution, Nernst-Planck Interface

Electrodes in the Electroanalysis Interface

The activation overpotential at an electrode–electrolyte interface with respect to the
electrode reaction m is defined as:

η m = φ s – φ l – E eq, m

This is the potential difference perceived by a redox couple, measured against the
equilibrium potential of the couple; it provides the thermodynamic driving force for
an electrochemical reaction by faradaic charge transfer between the electrode and the
electrolyte domains.

Subject to the approximation of constant electrolyte potential (φl = 0), this equation
reduces to:

η m = φ s – E eq, m

The activation overpotential is independent of the properties of the adjacent

electrolyte. It only depends on the applied electrode potential φs and the equilibrium
potential of the redox couple, where both are measured against a common reference
potential.

THEORY FOR THE ELECTROANALYSIS INTERFACE | 135

 The current density due to an electrode reaction at a point on an electrode surface is
computed using an electrochemical rate expression. For most practical electroanalytical
applications, the rate depends on the local concentration which varies during the study,
and so the most relevant expression is The Electroanalytical Butler–Volmer Equation.

Electrode Kinetics Expressions

The flux Ni of the chemical species i (SI unit: mol/m2) across an electrode surface
depends on the current densities im associated with the electrode reactions m
according to Faraday’s laws of electrolysis. These can be written as:

ν i, m i m
Ni =  -----------------
nm F
- (3-12)
m

where νi,m is the stoichiometric coefficient of species i with respect to reaction m (in
the reductive direction), and nm is the number of electrons transfered. F is the
Faraday constant which is the charge on a mole of electrons (= 96485.3365 C/mol).

The surface flux is applied as a boundary condition:

Ni = Ni ⋅ n (3-13)

Equation 3-12 and Equation 3-13 constitute the coupling between charge balance
and mass balance in the Electroanalysis interface. This coupling only applies at the
electrode–electrolyte interface, which is a boundary to the domain where the
Electroanalysis solves for chemical species transport.

The total current density is the sum of Faradaic (electrode reaction) components and
non-Faradaic components (inf) such as current due to Double Layer Capacitance:

i total =  iloc, m + inf

m

The experimentally measurable total current I (SI unit: A) drawn at an electrode can
be computed by integration of the local current density (SI unit: A/m2) across the
electrode area:

136 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

 I total =  itotal ds
∂Ω

Domain Equations for the Electroanalysis Interface

The Electroanalytical Butler–Volmer Equation

A one-electron electrochemical reaction between two solution-phase species can be
–
written as a reduction Ox + e ↔ Red .

Ox and Red represent the oxidized and reduced forms of the chemical species,
respectively.

The most general equation to describe the rate of this reaction as it proceeds at an
electrode surface is the electroanalytical Butler–Volmer equation:

α a Fη – α c Fη
i loc = k 0 F  c Red exp  --------------- – c Ox exp  -----------------  (3-14)
RT RT

where k0 is the heterogeneous rate constant (SI unit: m/s) and αc is the (cathodic)
transfer coefficient (dimensionless). For a one-electron reduction, the anodic and
cathodic transfer coefficients are related as follows α a + α c = 1 .

When the current is zero, the electroanalytical Butler–Volmer equation can be

rearranged to the thermodynamic Nernst equation relating the equilibrium
concentrations of the reacting species:

– FE eq
c Red = c Ox exp  ----------------
 RT 

Where the flux of the reacting species is negligible compared to the concentration of
these species, the concentrations are roughly constant (cRed ~ cOx ~ c). This converts
Equation 3-14 into the Butler–Volmer equation written in terms of an exchange
current density i0 (SI unit: A/m2):

α a Fη – α c Fη
i loc = i 0  exp  --------------- – exp  ----------------- 
  RT   RT  

The exchange current density i0 (SI unit: A/m2) is then related to the heterogeneous
rate constant as i 0 = k 0 Fc .

THEORY FOR THE ELECTROANALYSIS INTERFACE | 137

 Counter Electrodes and Overall Charge Balance
The Electroanalysis interface does not solve explicitly for the electrolyte potential in
the domains. This has the implication that an overall charge balance of a modeled cell
does not follow naturally as a result of the domain potential equation (as is the case for
instance when solving for Ohm’s law in the Secondary Current Distribution interface).

In order to model a charge balance of a cell with an arbitrary number of working

electrodes and counter electrodes, the solution is to add an extra degree of freedom
for the counter electrode potential, φs, CE, and then solve for this potential to fulfill the
following current balance over all electrode surfaces:

φ s, CE :  i tot dS = 0 (3-15)
electrodes

The counter electrode potential is used in the overpotential, η, in the kinetics

expression(s) on the counter electrode.

η m = φ s, CE – E eq, m (3-16)

Note that only one counter electrode potential degree of freedom is added in the
Electroanalysis interface, regardless of the number of counter electrodes that are active.

Domain Equations for the Electroanalysis Interface

138 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Electrode Potentials and Reference
E le c t r o de s
In all the Electrochemistry branch interfaces, the dependent potential variables are φ s
(SI unit: V), the electric potential of the electrode phase (the electron conductor, such
as metal), and φ l (SI unit: V), the potential of the electrolyte phase (ion conductor).

Typically the kinetics of the electrochemical reactions are defined using the
overpotential, η (SI unit: V), defined as

η = φ s – φ l – E eq (3-17)

where Eeq (SI unit: V) is the equilibrium potential. If it is to apply for all
overpotentials, a general kinetic expression for an electrode reaction must be set up so
that the charge-transfer current over the electrolyte-electrode interface is zero for zero
overpotential (equilibrium conditions).

An implication of Equation 3-17 is that it is the potential difference, φ s – φ l , that

governs the kinetics, not the absolute individual values of φ s and φ l. A global change
in the reference for both potentials has no impact on the electrode kinetics. As a result
of this, the potentials have to be “boot-strapped” in a model in some way, typically by
making an arbitrary choice of electric ground — for example, on an external boundary
— in order to ensure that there is a unique solution to the problem.

In this section:

• Reference Electrodes
• Boundary Conditions Using Reference Electrode Potentials
• Nodes for Handling Electrode Potentials and Reference Electrodes

Reference Electrodes
In experimental electrochemistry, it is common to use a reference electrodes when
controlling current or voltage with a potentiostat. Potential differences in the system
are recorded with respect to the equilibrium potential of the redox couple at the
reference electrode. A good reference electrode is designed so that no net charge
transfer takes place at its electrode-electrolyte interface. Then the overpotential of the
reference is zero, so:

ELECTRODE POTENTIALS AND REFERENCE ELECTRODES | 139

 φ s, ref = φ l + E eq, ref (3-18)

where φ s , ref (SI unit: V) is the electric potential of the reference electrode and Eeq, ref
(SI unit: V) is the equilibrium potential of the reference electrode reaction.

The electric potentials of the electrodes in the electrochemical cell can then be defined
with respect to the reference electrode according to:

E vs ref = φ s – φ s, ref (3-19)

where Evs ref (SI unit: V) is the electrode potential versus the reference potential.

It is important to realize that the presence of an ideal reference electrode in the system
has no impact on the physics; the only purpose of the reference electrode is to define
a stable reference point for the potential levels.

Boundary Conditions Using Reference Electrode Potentials

The set of boundary conditions defined in a model of an electrochemical cell needs to
ensure that no current flows through the reference electrode. A constraint for the
potential on the actual reference electrode is not suitable in general since it can create
unwanted local sources or sinks of current.

When modeling the control of an electrochemical cell by a potentiostat, which

monitors and controls the potential of an electrodes versus a reference electrode, the
electric potential conditions should be applied to the boundaries over which the
current flows in the cell. One electrode (the counter electrode) is typically grounded,
whereas an electric potential condition is set on all other (working) electrode
boundaries according to

φ s, bnd = E vs ref + φ s, ref (3-20)

where φ s , bnd (SI unit: V) is the applied electric boundary potential on the electrode.

Nodes for Handling Electrode Potentials and Reference Electrodes

The Reference Electrode node is a point feature applicable to electrolyte domains (in
all the Electrochemistry interfaces). It defines a global electric reference potential
φ s , ref (SI unit: V) according to Equation 3-18. The φ s , ref can be used in the
Electrode Potential feature for setting the electric potential of an electrode boundary
with respect to the reference potential. The variable Evs ref (SI unit: V), according to
Equation 3-19, is also defined in all electrode domains.

140 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

The Electric Reference Potential node is a point feature applicable to electrode
domains (in all the Electrochemistry interfaces). It defines a global electric reference
potential φ s , ref (SI unit: V) equal to the dependent variable φ s (SI unit: V) in the
point. The φ s , ref can be used in the Electrode Potential feature for setting the electric
potential of an electrode boundary with respect to the reference potential.

Whenever a φ s , ref is defined, the variable Evs ref (SI unit: V), according to
Equation 3-19, is also defined in all electrode domains.

The Electrode Potential is a boundary condition feature, applicable to external

boundaries of electrode domains (in all the Electrochemistry interfaces). It sets a
boundary condition for the electric potential with respect to a defined reference
potential according to Equation 3-20. Electric potentials defined by the Electric
Reference Potential and Reference Electrode point feature can be used as input when
specifying the Electrode Potential feature.

An Electrode Potential alternative in the Boundary Condition settings list is also

available for the Electrode Surface node.

The variable Evs ref (SI unit: V), according to Equation 3-19, is also defined on these
features.

ELECTRODE POTENTIALS AND REFERENCE ELECTRODES | 141

 S o lv i ng E le c tr och emi cal Mod el s
Due to the highly nonlinear nature of electrode kinetics, some electrochemical models
can be difficult to solve. This section includes some general tips and tricks to facilitate
model solving, trouble shooting, and to improve solution accuracy.

Studies and Solvers and Building a COMSOL Multiphysics Model in the

COMSOL Multiphysics Reference Manual

General Current Distribution Problems

Start with the following suggestions if you encounter difficulty solving a problem.

• Make sure that the potential levels are boot-strapped somewhere in the model,
preferably by grounding one electrode.
• Consider using a Stationary with Initialization or a Time-dependent with Initialization
study. Both these studies will use a Current Distribution Initialization study step as a
first step to solve for the potentials only. If you run into problems solving for the
second step in this study you may have to change the Current distribution type
setting to Secondary on the Current Distribution Initialization study step node, and
also review the Initial Values as described in the next bullet.
• Review the Initial Values, especially the potentials. Suitable initial potential values can
usually be derived making a “potential walk” through the geometry, starting at the
grounded boundary expected to deviate the least from equilibrium (usually the one
with the fastest kinetics, for instance the hydrogen electrode in a PEM fuel cell) and
assuming zero overpotentials for the main electrode reactions.
• Switch to Linearized Butler-Volmer kinetics while troubleshooting. This can be useful
to help achieve a solution for a model that does not solve with nonlinear kinetics,
thereby indicating suitable initial values for the nonlinear problem.
• If your model contains porous electrodes, try refining the mesh resolution in these
domains, especially towards the electrolyte boundaries.

• Electrochemistry Interfaces
• Specifying Initial Values and Meshing Techniques in the COMSOL
Multiphysics Reference Manual

142 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Electrochemistry Coupled to Mass Transport
If the model involves electrochemistry coupled to mass transport, here are a few things
to try to help improve model convergence.

• Review the Initial Values for the concentration values. Zero initial concentration
values can cause issues in tertiary current distributions and battery simulations since
that could imply that no charge carriers or no reacting material is present initially.
• If steep concentration gradients are expected close to electrode surfaces, use
boundary layer meshing or finer size settings at these boundaries.
• When setting up user-defined kinetics expressions, avoid evaluating negative
concentrations by using expressions such as max(c, eps^2), where eps is the
machine epsilon, that is, a very small number.
• Try to solve for low currents / low overpotentials first, then increase the cell load
(for stationary problems this can be done using an auxiliary sweep with
continuation).
• If a problem involving mass transport is hard to solve for high currents, but solves
for low currents, it might be due to mass transport limitations. In this case, review
the transport parameter values and check that the current magnitudes are
reasonable. If the current densities are unreasonably high, review the electrode
reaction settings.

• Electrochemistry Interfaces
In the COMSOL Multiphysics Reference Manual:

• 2D and 3D Boundary Layer Meshes

• Stationary and Parametric Sweep

Setting up a Study Sequence for Multiphysics Problems

For multiphysics problems, try to adjust the study sequence.

• Solve certain physics interfaces in a sequence. This can in many cases reduce
computational time and improve convergence. Analyzing the results when solving a
physics interface separately can also help when trouble-shooting a non-converging
model.
• A good strategy is often to solve for the potentials only (that is, disable mass
transport and flow interfaces), using a stationary study step, before solving the full

SOLVING ELECTROCHEMICAL MODELS | 143

 model in the study sequence. In this way the stationary solution is used as initial
values for the following steps. This can be manually by modifying the settings of the
study node, or in an automated way by using the using Stationary with Initialization
or a Time-dependent with Initialization study as described above.
• In many models the flow profile is only slightly (or not at all) affected by changes in
current density. Therefore it can be a good strategy to separately solve for the flow
early in the study sequence, and then solve for the other physics interfaces in the
subsequent steps. (If the flow is not affected at all by the current distribution,
solving for the flow can be disabled entirely in consecutive steps).

• Electrochemistry Interfaces
In the COMSOL Multiphysics Reference Manual:

• Studies and Solvers

• Analyzing Model Convergence and Accuracy
• Achieving Convergence When Solving Nonlinear Equations

Time-dependent Problems with Load Steps

For time-dependent problems, try the following to mitigate accuracy and convergence
issues with regards to sudden current or potential load steps.

• Use smoothed current/potential load functions in order to avoid discrete load

steps.
• Add a double layer capacitance to the model, which can improve the numerical
stability.
• Reduce the Maximum step taken by the solver if you want to prevent the solver from
“missing” short square load steps, or change the Steps taken by solver setting from
Free to Strict, or Intermediate, to control the time steps using the Times text field.
Using the Events interface can also be an option in certain cases if the load cycle
itself varies dynamically.

• Double Layer Capacitance

In the COMSOL Multiphysics Reference Manual:

• Step and Time Dependent

• Building a COMSOL Multiphysics Model and The Events Interface

144 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Solver Settings
Try adjusting the solver settings.

• In rare cases, try to increase the Maximum number of iterations.

• If you know the order of magnitude of the dependent variables beforehand, setting
the scaling method to Manual for these can improve convergence and the accuracy
of the results.

In the COMSOL Multiphysics Reference Manual:

• Studies and Solvers

• Analyzing Model Convergence and Accuracy
• Achieving Convergence When Solving Nonlinear Equations

SOLVING ELECTROCHEMICAL MODELS | 145

146 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES
 4

Chemical Species Transport Interfaces

This chapter describes the physics interfaces found under the Chemical Species
Transport branch ( ). The chapter summarizes each physics interface including
the different fields, material properties, and boundary conditions associated with
them, and suggests how and when to apply it.

In this chapter:

• The Transport of Diluted Species Interface

• The Chemistry Interface
• The Nernst-Planck-Poisson Equations Interface
• The Electrophoretic Transport Interface
• The Surface Reactions Interface
• Theory for the Transport of Diluted Species Interface
• Theory for the Electrophoretic Transport Interface
• Theory for the Surface Reactions Interface
• Theory for the Coupling of Mass Transport to Electrochemical Reactions

147
 T he T r a ns po r t of D i l u t ed Sp eci es
Interface
The Transport of Diluted Species (tds) interface ( ), found under the Chemical Species
Transport branch ( ), is used to calculate the concentration field of a dilute solute in
a solvent. Transport and reactions of the species dissolved in a gas, liquid, or solid can
be handled with this interface. The driving forces for transport can be diffusion by
Fick’s law, convection when coupled to a flow field, and migration, when coupled to
an electric field.

The interface supports simulation of transport by convection and diffusion in 1D, 2D,
and 3D as well as for axisymmetric components in 1D and 2D. The dependent variable
is the molar concentration, c. Modeling multiple species transport is possible, whereby
the physics interface solves for the molar concentration, ci, of each species i.

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is tds.

DOMAIN SELECTION
If any part of the model geometry should not partake in the mass transfer model,
remove that part from the selection list.

TRANSPORT MECHANISMS
Mass transport due to diffusion is always included. Use the check boxes available under
Additional transport mechanisms to control other transport mechanisms.

148 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Note: Some of the additional transport mechanisms listed below are available in all
products. For details see http://www.comsol.com/products/specifications/.

• By default, the Convection check box is selected. Clear the check box to disable
convective transport.
• Select the Migration in electric field check box to activate transport of ionic species in
an electric field. See further the theory section Adding Transport Through
Migration.

Transport of ionic species in an electric field is available in a limited set of

add-on products. See http://www.comsol.com/products/
specifications/ for more details on availability.

Mass Transport in Porous Media

The Mass transport in porous media check box activates functionality specific to species
transport in porous media. When selected, the following transport mechanisms are
available:

• Select the Dispersion in porous media check box to activate the dispersion mechanism
in porous media. See further Dispersion in the theory chapter.
• Select the Volatilization in partially saturated porous media check box to model
volatilization in partially saturated domains. See further Theory for the Transport of
Diluted Species Interface.

The following features are also enabled when selecting the Mass transport in porous
media check box:

• Adsorption
• Partially Saturated Porous Media
• Porous Electrode Coupling
• Porous Media Transport Properties

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 149

 CONSISTENT STABILIZATION
To display this sections, click the Show button ( ) and select Stabilization.

• When the Crosswind diffusion check box is selected, a weak term that reduces
spurious oscillations is added to the transport equation. The resulting equation
system is always nonlinear. There are two options for the Crosswind diffusion type:
- Do Carmo and Galeão — the default option. This type of crosswind diffusion
reduces undershoots and overshoots to a minimum but can in rare cases give
equation systems that are difficult to fully converge.
- Codina. This option is less diffusive compared to the Do Carmo and Galeão
option but can result in more undershoots and overshoots. It is also less effective
for anisotropic meshes. The Codina option activates a text field for the Lower
gradient limit glim. It defaults to 0.1[mol/m^3)/tds.helem, where tds.helem
is the local element size.
• For both consistent stabilization methods, select an Equation residual. Approximate
residual is the default and means that derivatives of the diffusion tensor components
are neglected. This setting is usually accurate enough and is computationally faster.
If required, select Full residual instead.

INCONSISTENT STABILIZATION
To display this section, click the Show button ( ) and select Stabilization. By default,
the Isotropic diffusion check box is not selected, because this type of stabilization adds
artificial diffusion and affects the accuracy of the original problem. However, this
option can be used to get a good initial guess for underresolved problems.

ADVANCED SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.
Normally these settings do not need to be changed. Select a Convective term—
Nonconservative form (the default) or Conservative form. The conservative formulation
should be used for compressible flow. See Convective Term Formulation for more
information.

DISCRETIZATION
The Compute boundary fluxes check box is activated by default so that COMSOL
Multiphysics computes predefined accurate boundary flux variables. When this option
is checked, the solver computes variables storing accurate boundary fluxes from each
boundary into the adjacent domain.

150 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

If the check box is cleared, the COMSOL Multiphysics software instead computes the
flux variables from the dependent variables using extrapolation, which is less accurate
in postprocessing results but does not create extra dependent variables on the
boundaries for the fluxes.

The flux variables affected in the interface are:

• ndflux_c (where c is the dependent variable for the concentration). This is the
normal diffusive flux and corresponds to the boundary flux when diffusion is the
only contribution to the flux term.
• ntflux_c (where c is the dependent variable for the concentration). This is the
normal total flux and corresponds to the boundary flux plus additional transport
terms, for example, the convective flux when you use the nonconservative form.

Also the Apply smoothing to boundary fluxes check box is available if the previous check
box is checked. The smoothing can provide a more well-behaved flux value close to
singularities.

For details about the boundary fluxes settings, see Computing Accurate Fluxes in the
COMSOL Multiphysics Reference Manual.

The Value type when using splitting of complex variables setting should in most pure
mass transfer problems be set to Real, which is the default. It makes sure that the
dependent variable does not get affected by small imaginary contributions, which can
occur, for example, when combining a Time Dependent or Stationary study with a
frequency-domain study. For more information, see Splitting Complex-Valued
Variables in the COMSOL Multiphysics Reference Manual.

DEPENDENT VARIABLES
The dependent variable name is the Concentration c by default. The names must be
unique with respect to all other dependent variables in the component.

Add or remove species variables in the model and also change the names of the
dependent variables that represent the species concentrations.

Enter the Number of species. Use the Add concentration ( ) and Remove
concentration ( ) buttons as needed.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 151

 FURTHER READING

• Theory for the Transport of Diluted Species Interface

• Numerical Stabilization in the COMSOL Multiphysics Reference
Manual.
• In the COMSOL Multiphysics Reference Manual, see Table 2-3 for
links to common sections and Table 2-4 for common feature nodes.
You can also search for information: press F1 to open the Help window
or Ctrl+F1 to open the Documentation window.

• Effective Diffusivity in Porous Materials: Application Library path

COMSOL_Multiphysics/Diffusion/effective_diffusivity
• Micromixer: Application Library path COMSOL_Multiphysics/
Fluid_Dynamics/micromixer

The Transport of Diluted Species in Porous Media Interface

This interface ( ), found under the Chemical Species Transport branch ( ), is used
to calculate the species concentration and transport in free and porous media. The
interface is the same as the Transport of Diluted Species interface but it uses other
defaults: The Mass Transport in Porous Media property is selected, and a Porous
Media Transport Properties node is added by default. The interface includes reaction
rate expressions and solute sources for modeling of species transport and reaction in
porous media.

This interface is dedicated to modeling transport in porous media, including immobile

and mobile phases, where the chemical species may be subjected to diffusion,
convection, migration, dispersion, adsorption, and volatilization in porous media. It
supports cases where either the solid phase substrate is exclusively immobile, or when
a gas-filling medium is also assumed to be immobile.

It applies to one or more diluted species or solutes that move primarily within a fluid
that fills (saturated) or partially fills (unsaturated) the voids in a solid porous medium.
The pore space not filled with fluid contains an immobile gas phase. Models including
a combination of porous media types can be studied.

The main feature nodes are the Porous Media Transport Properties and Partially
Saturated Porous Media nodes, which add the equations for the species concentrations

152 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

and provide an interface for defining the properties of the porous media, as well as
additional properties governing adsorption, volatilization, dispersion and diffusion,
migration, and the velocity field to model convection.

The physics interface can be used for stationary and time-dependent analysis.

When this physics interface is added, these default nodes are also added to the Model
Builder — Porous Media Transport Properties, No Flux (the default boundary condition),
and Initial Values. Then, from the Physics toolbar, add other nodes that implement, for
example, boundary conditions, reaction rate expressions, and species sources. You can
also right-click Transport of Diluted Species in Porous Media to select physics features
from the context menu.

SETTINGS
The rest of the settings are the same as The Transport of Diluted Species Interface.

FURTHER READING

• Theory for the Transport of Diluted Species Interface

• Domain, Boundary, and Pair Nodes for the Transport of Diluted
Species Interface

• Variably Saturated Flow and Transport — Sorbing Solute:

Application Library path Subsurface_Flow_Module/Solute_Transport/
sorbing_solute
Web link: http://www.comsol.com/model/
variably-saturated-flow-and-transport-sorbing-solute-490

Domain, Boundary, and Pair Nodes for the Transport of Diluted

Species Interface
The Transport of Diluted Species Interface has the following domain, boundary, and
pair nodes, listed in alphabetical order, available from the Physics ribbon toolbar

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 153

 (Windows users), Physics context menu (Mac or Linux users), or by right-clicking to
access the context menu (all users).

To add a node, go to the Physics toolbar, no matter what operating system

you are using. Subnodes are available by clicking the parent node and
selecting it from the Attributes menu.

• Adsorption • Periodic Condition

• Concentration • Point Mass Source
• Electrode Surface Coupling • Porous Electrode Coupling
• Equilibrium Reaction • Porous Media Transport Properties
• Fast Irreversible Surface Reaction • Reaction Coefficients
• Flux • Reactions
• Flux Discontinuity • Reactive Pellet Bed
• Fracture • Species Source
• Inflow • Surface Reactions
• Initial Values • Surface Equilibrium Reaction
• Line Mass Source • Symmetry
• Mass-Based Concentrations • Thin Diffusion Barrier
• No Flux • Thin Impermeable Barrier
• Open Boundary • Transport Properties
• Outflow • Turbulent Mixing
• Partially Saturated Porous Media • Volatilization
• Partition Condition

Some features require certain add-on modules. See details http://

www.comsol.com/products/specifications/

For axisymmetric components, COMSOL Multiphysics takes the axial

symmetry boundaries (at r = 0) into account and automatically adds an
Axial Symmetry node that is valid on boundaries representing the
symmetry axis.

154 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

 In the COMSOL Multiphysics Reference Manual, see Table 2-3 for links
to common sections and Table 2-4 for common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Transport Properties
The settings in this node are dependent on the check boxes selected under Transport
Mechanisms on the Settings window for the Transport of Diluted Species interface. It
includes only the sections required by the activated transport mechanisms. It has all the
equations defining transport of diluted species as well as inputs for the material
properties.

When the Convection check box is selected, the Turbulent Mixing subnode is available
from the context menu as well as from the Physics toolbar, Attributes menu.

MODEL INPUTS
The temperature model input is always available. Select the source of the Temperature.
For User defined, enter a value or expression for the temperature in the input field. This
input option is always available.

You can also select the temperature solved for by a Heat Transfer interface added to
the model component. These physics interfaces are available for selection in the
Temperature list.

CONVECTION
If transport by convection is active, the velocity field of the solvent needs to be
specified. Select the source of the Velocity field. For User defined, enter values or
expressions for the velocity components in the input fields. This input option is always
available.

You can also select the velocity field solved for by a Fluid Flow interface added to the
model component. These physics interfaces are available for selection in the Velocity
field list.

DIFFUSION
Select an option from the Material list. This selection list can only be used if a material
has been added in the Materials node and if that material has a diffusion coefficient
defined. Else, you need to type in the diffusivity in the User Defined edit field.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 155

 Enter the Diffusion coefficient Dc for each species. This can be a scalar value for isotropic
diffusion or a tensor describing anisotropic diffusion. Select the appropriate tensor
type — Isotropic, Diagonal, Symmetric, or Anisotropic that describes the diffusion
transport, and then enter the values in the corresponding element (one value for each
species).

Note that multiple species, as well as Migration in Electric fields (described below) is
only available for certain COMSOL Multiphysics add-on products. See details: http:/
/www.comsol.com/products/specifications/.

MIGRATION IN ELECTRIC FIELD

This section is available when the Migration in electric field check box is selected. From
the Electric potential list, select the source of the electric field.

• Enter a value or expression for the Electric potential V, which is User defined; this
input option is always available.
• Select the electric potential solved by an AC/DC-based interface that has also been
added to the model.
• Select the electric potential defined or solved by Electrochemistry interface that has
been added to the component.

By default the Mobility is set to be calculated based on the species diffusivity and the
temperature using the Nernst-Einstein relation. For User defined, and under Mobility,
select the appropriate scalar or tensor type — Isotropic, Diagonal, Symmetric, or
Anisotropic — and type in the value of expression of the mobility um,c.

Enter the Charge number zc (dimensionless, but requires a plus or minus sign) for each
species.

The temperature (if you are using mobilities based on the Nernst-Einstein relation) is
taken from Model Inputs section.

Note that the migration in electric fields feature is only available in some COMSOL
products. See details: http://www.comsol.com/products/specifications/.

156 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

EXAMPLE MODELS

• Separation Through Dialysis: Application Library path

Chemical_Reaction_Engineering_Module/Mixing_and_Separation/dialysis
Web link: http://www.comsol.com/model/
separation-through-dialysis-258

• Transport in an Electrokinetic Valve: Application Library path

Microfluidics_Module/Fluid_Flow/electrokinetic_valve
Web link: http://www.comsol.com/model/electrokinetic-valve-603

Turbulent Mixing
Use this node to account for the turbulent mixing of the chemical species caused by
the eddy diffusivity. This node should typically be used when the specified velocity field
corresponds to a RANS solution.

This feature is only available in a limited set of add-on products. See

http://www.comsol.com/products/specifications/ for more details on
availability.

The subnode can added from the context menu (right-click the Transport Properties
parent node), as well as from the Physics toolbar, Attributes menu, provided that
Convection is selected as a transport mechanism.

TURBULENT MIXING PARAMETERS

Some physics interfaces provide the turbulent kinematic viscosity, and these appear as
options in the Turbulent kinematic viscosity νT list. The list always contains the User
defined option where any value or expression can be entered.

The default Turbulent Schmidt number ScT is 0.71 (dimensionless).

FURTHER READING
See the section About Turbulent Mixing in the CFD Module User’s Guide (this link
is available online or if you have the CFD Module documentation installed).

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 157

 Initial Values
The Initial Values node specifies the initial values for the concentration of each species.
These serve as an initial guess for a stationary solver or as initial conditions for a
transient simulation.

DOMAIN SELECTION
If there are several types of domains with different initial values defined, it might be
necessary to remove some domains from the selection. These are then defined in an
additional Initial Values node.

INITIAL VALUES
Enter a value or expression for the initial value of the Concentration or concentrations,
ci. This also serves as a starting guess for stationary problems.

Mass-Based Concentrations
Use the Mass-Based Concentrations node to add postprocessing variables for mass-based
concentrations (SI unit: kg/m3) and mass fractions (dimensionless) for all species.

MIXTURE PROPERTIES
The default Solvent density ρsolvent is taken From material. For User defined, enter a
value or expression manually. Define the Molar mass of each species, which is needed
to calculate the mass-based concentration.

Reactions
Use the Reactions node to account for the consumption or production of species
through chemical reactions. Define the rate expressions as required.

DOMAIN SELECTION
From the Selection list, choose the domains on which to define rate expression or
expressions that govern the source term in the transport equations.

Several reaction nodes can be used to account for different reactions in different parts
for the modeling geometry.

REACTION RATES
Add a rate expression Ri (SI unit: mol/(m3·s)) for species i. Enter a value or expression
in the field. Note that if you have the Chemistry interface available, provided with the

158 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Chemical Reaction Engineering Module, the reaction rate expressions can be
automatically generated and picked up using the drop-down menu. For an example,
see the application Fine Chemical Production in a Plate Reactor as linked below.

REACTING VOLUME
This section is only available when the Mass Transport in Porous Media property is
available and selected. See http://www.comsol.com/products/specifications/ for
more details on availability.

When specifying reaction rates for a species in porous media, the specified reaction rate
may have the basis of the total volume, the pore volume, or the volume of a particular
phase.

• For Total volume, the reaction expressions in mol/(m3·s) are specified per unit
volume of the model domain (multiplied by unity).
• For Pore volume, the reaction expressions in mol/(m3·s) are specified per unit
volume of total pore space. The reaction expressions will be multiplied by the
domain porosity, εp. (εp equals unity for nonporous domains.)
• For Liquid phase, the reaction expressions in mol/(m3·s) are specified per unit
volume of liquid in the pore space. The expressions will be multiplied by the liquid
volume fraction θ. (θ equals εp for Saturated Porous Media domains).
• For Gas phase, the expressions are multiplied by the gas volume fraction av = εp − θ.
av equals 0 for Saturated Porous Media domains.

FURTHER READING
See the theory chapter on chemical species transport, starting with the section Mass
Balance Equation.

• Fine Chemical Production in a Plate Reactor: Application Library

path Chemical_Reaction_Engineering_Module/
Reactors_with_Mass_and_Heat_Transfer/plate_reactor
Web link: http://www.comsol.com/model/
fine-chemical-production-in-a-plate-reactor-8589

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 159

 No Flux
This node is the default boundary condition on exterior boundaries. It should be used
on boundaries across which there is no mass flux, typically exterior solid walls where
no surface reactions occur. The condition applied for each species corresponds to

–n ⋅ Ji = 0

Inflow
Use this node to specify all species concentrations at an inlet boundary.

If you want to specify the concentration of a subset of the partaking species, this can
be done by using the Concentration node instead.

For the Electroanalysis interface, this node is available when you select the Convection
check box on the physics interface Settings window.

CONCENTRATION
For the concentration of each species c0,c (SI unit: mol/m3), enter a value or
expression.

BOUNDARY CONDITION TYPE

This section in the settings is only available for some products. Search for “Inflow” on
the page: http://www.comsol.com/products/specifications/ for more details on
availability.

The option Concentration constraint constrains the concentration values on the

boundary by the use of pointwise constraints. The other option, Flux (Danckwerts) can
be more stable and fast to solve when high reaction rates are anticipated in the vicinity
of the inlet. Oscillations on the solutions can also be avoided in such cases. The latter
condition uses a flux boundary condition based on the velocity across the boundary
and the concentration values. See further details in the theory section.

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.
You can find details about the different constraint settings in the section Constraint
Reaction Terms in the COMSOL Multiphysics Reference Manual.

FURTHER READING
See the theory chapter in the section Danckwerts Inflow Boundary Condition.

160 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Outflow
Apply this condition at outlets boundaries where species should be transported out of
the model domain by fluid motion or by an electric field (in the case of ions). It is
assumed that convection and migration in an electric are the dominating transport
mechanisms across the boundary, and therefore that the diffusive transport can be
ignored, that is:

n ⋅ ( – D ∇c ) = 0

Note that the Convection or the Migration in electric field transport mechanisms needs
to be included for this node to be available.

Concentration
This condition node adds a boundary condition for the species concentration. For
example, a c = c0 condition specifies the concentration of species c.

CONCENTRATION
Individually specify the concentration for each species. Select the check box for the
Species to specify the concentration, and then enter a value or expression in the
corresponding field. To use another boundary condition for a specific species, click to
clear the check box for the concentration of that species.

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.
You can find details about the different constraint settings in the section Constraint
Reaction Terms in the COMSOL Multiphysics Reference Manual.

Flux
This node can be used to specify the species flux across a boundary. The prescribed flux
of a species c is defined as:

– n ⋅ ( – D∇c ) = J 0

When the mass transport includes migration of ionic species, the flux is defined as:

– n ⋅ ( – D∇c – zu m Fc∇φ ) = J 0

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 161

 The flux prescribed, J0, is an arbitrary user-specified flux expression. It can for example
represent a flux due to chemical reactions or phase change, or the transport to or from
a surrounding environment currently not included model. J0 can be constant or a
function of the any dependent variable, for example the concentration, temperature,
pressure or the electric potential φ.

INWARD FLUX
Select the Species check box for the species to specify and enter a value or expression
for the inward flux in the corresponding field. Use a minus sign when specifying a flux
directed out of the system. To use another boundary condition for a specific species,
click to clear the check box for that species.

External convection
Set Flux type to External convection to prescribe a flux to or from an exterior domain
(not modeled) assumed to include convection. The exterior can for example include a
forced convection to control the temperature or to increase the mass transport. In this
case the prescribed mass flux corresponds to

J0 = kc ( cb – c )

where kc is a mass transfer coefficient and cb is the bulk concentration, the typical
concentration far into the surrounding exterior domain.

Symmetry
The Symmetry node can be used to represent boundaries where the species
concentration is symmetric, that is, where there is no mass flux across the boundary.

This boundary condition is identical to that of the No Flux node.

Flux Discontinuity
This node represents a discontinuity in the mass flux across an interior boundary:

– n ⋅ [ ( J + uc ) u – ( J + uc ) d ] = N 0 J = – D∇c – zu m Fc∇φ

where the value N0 (SI unit: mol/(m2·s)) specifies the jump in total flux at the
boundary. This can be used to model a boundary source, for example a surface
reaction, adsorption or desorption.

162 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

FLUX DISCONTINUITY
In this section the jump in species flux (or surface source) is specified.

Select the Species check box for the species to specify and enter a value or expression
for the material flux jump in the corresponding field. To use a different boundary
condition for a specific species, click to clear the check box for the flux discontinuity
of that species.

Partition Condition
The Partition Condition node can be used to prescribe the ratio between the
concentration of a solute species in two different immiscible phases. It can for example
be used on interior boundaries separating two liquid phases, a gas-liquid interface, or
on a boundary separating a liquid phase and a solid or porous media. For a species
concentration ci, the ratio between the concentration on the up side and on the down
side of the boundary (ci,u and ci,d respectively) is defined as

c i, u
K i = ---------
c i, d

in terms of a partition coefficient Ki. The up and down side of the selected boundary
is indicated in the Graphics window. The arrows point from the down side into the up
side.

This feature is only available in a limited set of add-on products. See

http://www.comsol.com/products/specifications/ for more details on
availability.

PARTITION COEFFICIENT
Select the Reverse direction check box to reverse the direction of the arrows on the
selected boundaries, and the corresponding definition of the up and down side
concentration.

Use the associated input fields to prescribe the partition coefficient Ki.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 163

 FURTHER READING
For an example of using a partition condition, see this application example:

Separation Through Dialysis: Application Library path

Chemical_Reaction_Engineering_Module/Mixing_and_Separation/dialysis

Periodic Condition
The Periodic Condition node can be used to define periodicity for the mass transport
between two sets of boundaries. The node prescribes continuity in the concentration
and the mass flux between the “source” and the “destination” side respectively. Note
that these names are arbitrary and does not influence the direction in which mass is
transported. It is dictated by mass transfer equations in the adjacent domains.

The node can be activated on more than two boundaries, in which case the feature tries
to identify two separate surfaces that each consist of one or several connected
boundaries.

For more complex geometries, it might be necessary to add the Destination Selection
subnode, which is available from the context menu (right-click the parent node) as well
as from the Physics toolbar, Attributes menu. With this subnode, the boundaries that
constitute the source and destination surfaces can be manually specified.

FURTHER READING
For an example of using a periodic condition, see this application example:

The KdV Equation and Solitons: Application Library path

COMSOL_Multiphysics/Equation_Based/kdv_equation

Line Mass Source

The Line Mass Source feature models mass flow originating from a tube or line region
with an infinitely small radius.

This feature is only available in a limited set of add-on products. See

http://www.comsol.com/products/specifications/ for more details on
availability.

164 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

SELECTION
The Line Mass Source feature is available for all dimensions, but the applicable selection
differs between the dimensions.

MODEL DIMENSION APPLICABLE GEOMETRICAL ENTITY

2D Points
2D Axisymmetry Points not on the symmetry axis and the symmetry axis
3D Edges

SPECIES SOURCE
·
Enter the source strength, q l,c , for each species (SI unit: mol/(m·s)). A positive value
results in species injection from the line into the computational domain, and a negative
value means that the species is removed from the computational domain.

Line sources located on a boundary affect the adjacent computational domains. This
effect makes the physical strength of a line source located in a symmetry plane twice
the given strength.

FURTHER READING
See the section Mass Sources for Species Transport.

Point Mass Source

The Point Mass Source feature models mass flow originating from an infinitely small
domain around a point.

This feature is only available in a limited set of add-on products. See

http://www.comsol.com/products/specifications/ for more details on
availability.

SPECIES SOURCE
·
Enter the source strength, q p,c , for each species (SI unit: mol/s). A positive value
results in species injection from the point into the computational domain, and a
negative value means that the species is removed from the computational domain.

Point sources located on a boundary or on an edge affect the adjacent computational

domains. This has the effect, for example, that the physical strength of a point source
located in a symmetry plane is twice the given strength.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 165

 FURTHER READING
See the section Mass Sources for Species Transport.

Open Boundary
Use this node to set up mass transport across boundaries where both convective inflow
and outflow can occur. On the parts of the boundary where fluid flows into the
domain, an exterior species concentration is prescribed. On the remaining parts, where
fluid flows out of the domain, a condition equivalent to the Outflow node is instead
prescribed.

The direction of the flow across the boundary is typically calculated by a fluid flow
interface and is provided as a model input to the Transport of Diluted Species
interface.

This feature is only available in a limited set of add-on products. See

http://www.comsol.com/products/specifications/ for more details on
availability.

EXTERIOR CONCENTRATION
Enter a value or expression for the Exterior concentration.

Thin Diffusion Barrier

Use this boundary condition to model a thin layer through which mass is transported
by diffusion only. The node is applicable on interior boundaries and can be used to
avoid meshing thin structures.

THIN DIFFUSION BARRIER

Specify the Layer thickness, ds, and input a Diffusion coefficient, Ds,c, for each of the
species included.

Thin Impermeable Barrier

This feature models a thin mass transfer barrier. It is available on interior boundaries
and introduces a discontinuity in the concentration across the boundary. On each side,
a no-flux condition is prescribed for the mass transport implying that it acts as a barrier.
The feature can be used to avoid meshing thin structures.

166 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Solving a model involving coupled fluid flow and mass transfer, the Thin Impermeable
Barrier feature can be combined with an Interior Wall feature in order to model a thin
solid wall.

Equilibrium Reaction
Use this node to model an equilibrium reaction, involving two or more species, in a
domain. Note that a necessary requirement for this is feature to be available is that two
or more species are solved for by the interface.

The equilibrium reaction is defined by the relation between the chemical activities of
the chemical species participating in the reaction (the equilibrium condition) and the
stoichiometry of the reaction.

The node solves for an additional degree of freedom (the reaction rate) to fulfill the
equilibrium condition at all times in all space coordinates.

If the Apply equilibrium condition on inflow boundaries check box is selected, the
specified inflow concentration values in all active Inflow boundary nodes for the physics
interface are modified to comply with the equilibrium condition.

This feature is only available in a limited set of add-on products. See

http://www.comsol.com/products/specifications/ for more details on
availability.

EQUILIBRIUM CONDITION
The list defaults to Equilibrium constant or select User defined. For either option, the
Apply equilibrium condition on inflow boundaries check box is selected by default.

For Equilibrium constant, enter an Equilibrium constant Keq (dimensionless). The

default is 1. Enter a value or expression for the Unit activity concentration Ca0 (SI
unit: mol/m3). The default is 1·10-3 mol/m3. Equilibrium constant creates an
equilibrium condition based on the stoichiometric coefficients, the species activities,
and the law of mass action.

For User defined, enter an Equilibrium expression Eeq (dimensionless).

STOICHIOMETRIC COEFFICIENTS
Enter a value for the stoichiometric coefficientνc (dimensionless). The default is 0. Use
negative values for reactants and positive values for products in the modeled reaction.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 167

 Species with a stoichiometric coefficient value of 0 are not affected by the Equilibrium
Reaction node.

FURTHER READING
See

• Equilibrium Reaction Theory

• Theory for the Coupling of Mass Transport to Electrochemical Reactions

Surface Reactions
The Surface Reactions node can be used to account for the species boundary flux due
to chemical reactions occurring on a surface (heterogeneous reactions). For a domain
species participating in a surface reaction, the boundary flux corresponds to the
reaction rate at the surface.

SURFACE REACTION RATE

Specify the surface reaction rate J0 of each species resulting from the reactions. Note
that if you have the Chemistry interface available, provided with the Chemical
Reaction Engineering Module, the reaction rate expressions can be automatically
generated and picked up using the drop-down menu.

FURTHER READING
For an example of using the Surface Reactions node, see this application example:

Chemical Vapor Deposition of GaAs: Application Library path

Chemical_Reaction_Engineering_Module/
Reactors_with_Mass_and_Heat_Transfer/gaas_cvd

Surface Equilibrium Reaction

Use this node to model an equilibrium reaction on a boundary (surface). The settings
for this node are similar to Equilibrium Reaction. Note that a necessary requirement

168 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

for this is feature to be available is that two or more species are solved for by the
interface.

This feature is only available in a limited set of add-on products. See

http://www.comsol.com/products/specifications/ for more details on
availability.

Fast Irreversible Surface Reaction

This boundary node defines an irreversible reaction where the kinetics is so fast that
the only factor limiting the reaction rate is the transport of a species to the reacting
surface.

The node will set the Rate limiting species concentration to zero at the boundary, and
balance the fluxes of the species participating in the reaction and the current densities
according to the Stoichiometric Coefficients settings.

This feature is only available in a limited set of add-on products. See

http://www.comsol.com/products/specifications/ for more details on
availability.

Porous Electrode Coupling

Use this node to add a molar source in a domain that is coupled to one or multiple
Porous Electrode ReactionElectrode Reaction nodes of an Electrochemistry Interface.

The molar source is calculated from the number of electrons, stoichiometric

coefficients, and volumetric current densities of the coupled porous electrode reactions
specified in the Reaction Coefficients subnodes.

In the Transport of Concentrated Species interface, the molar sources (or sinks) are
multiplied by the species molar masses to obtain the corresponding mass sources.

Additional Reaction Coefficients subnodes are available from the context menu
(right-click the parent node) as well as from the Physics toolbar, Attributes menu.

Note that if you are also modeling the momentum transport and expect a
non-negligible total mass source or sink, which is often the case in gas diffusion

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 169

 electrodes, you need to also add a corresponding Porous Electrode Coupling node in
the Fluid Flow interface.

This feature is only available in a limited set of add-on products. See

http://www.comsol.com/products/specifications/ for more details on
availability.

Reaction Coefficients
Add this node to the Electrode Surface Coupling and Porous Electrode Coupling
features to define molar fluxes and sources based on electrode current densities in an
Electrochemistry interface.

The molar flux or source is proportional to the stoichiometric coefficients and the
current density according to Faraday’s law.

Current densities from Electrode Reaction (iloc, SI unit: A/m2) or Porous Electrode
Reaction nodes (iv, SI unit: A/m3) of any Electrochemistry interface in the model are
available for selection as the Coupled reaction, and user-defined expressions are also
supported.

Enter the Number of participating electrons nm (dimensionless) and the Stoichiometric

coefficient vc (dimensionless) as explained in the theory section linked below.

Use multiple subnodes to couple to multiple reactions.

Theory for the Coupling of Mass Transport to Electrochemical Reactions

Electrode Surface Coupling

Use this node to define a flux boundary condition based on current densities of one or
multiple Electrode ReactionElectrode Reaction nodes in an Electrochemistry
interface.

The flux is proportional to the current densities and the stoichiometric coefficients
according to Faraday’s law as defined by summation over the Reaction Coefficients
subnodes.

170 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Note that if you are also modeling the momentum transport and expect a
non-negligible total mass flux over the boundary, which is often the case for gas
diffusion electrodes, you need to also add a corresponding Electrode Surface Coupling
node in the Fluid Flow interface.

This feature is only available in a limited set of add-on products. See

http://www.comsol.com/products/specifications/ for more details on
availability.

Porous Media Transport Properties

Use this node to model the concentration of diluted species transported through
interstices in porous media. A part form convection and diffusion, the node contains
functionality to include species evolution through adsorption, dispersion, and reaction.

This feature is only available in a limited set of add-on products. See

http://www.comsol.com/products/specifications/ for more details on
availability.

MODEL INPUTS
The temperature model input is always available. Select the source of the Temperature.
For User defined, enter a value or expression for the temperature in the input field. This
input option is always available.

You can also select the temperature solved for by a Heat Transfer interface added to
the model component. These physics interfaces are available for selection in the
Temperature list.

MATRIX PROPERTIES
Use the Porous material list to define a material specifying the matrix properties on the
current selection. By default the Domain material is used.

Specify the Porosity, εp (dimensionless) of the porous matrix. This is by default taken
From material. Select User defined to instead enter a different value.

CONVECTION
If transport by convection is active, the velocity field of the solvent needs to be
specified. Select the source of the Velocity field. For User defined, enter values or

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 171

 expressions for the velocity components in the input fields. This input option is always
available.

You can also select the velocity field solved for by a Fluid Flow interface added to the
model component. These physics interfaces are available for selection in the Velocity
field list.

DIFFUSION
Select a Fluid material (when available and applicable).

Specify the Fluid diffusion coefficient DF,i (SI unit: m2/s). Enter a value or expression
for each of the species in the corresponding input field. The default is 1·10-9 m2/s.

Select the Effective diffusivity model: Millington and Quirk model (the default),
Bruggeman model, Tortuosity model, or User defined. For Tortuosity model, enter a value
for the tortuosity τF,i (dimensionless). The default is 1.

MIGRATION IN ELECTRIC FIELD

This section is available when the Migration in electric field check box is selected. From
the Electric potential list, select the source of the electric field.

• Enter a value or expression for the Electric potential V, which is User defined; this
input option is always available.
• Select the electric potential solved by an AC/DC-based interface that has also been
added to the model.
• Select the electric potential defined or solved by Electrochemistry interface that has
been added to the component.

By default the Mobility is set to be calculated based on the species effective diffusivity
and the temperature using the Nernst-Einstein relation. For User defined, and under
Mobility, select the appropriate scalar or tensor type — Isotropic, Diagonal, Symmetric,
or Anisotropic — and type in the value of expression of the effective mobility ume,c.

Enter the Charge number zc for each species.

DISPERSION
This section is available when the Dispersion in porous media check box is selected on
the Settings window for the physics interface.

Select the Specify dispersion for each species individually check box to specify the
dispersion tensor DD (SI unit: m2/s) for each species separately. The default is to use
the same dispersion tensor DD for all species.

172 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Select an option from the Dispersion tensor list — User defined (the default) or
Dispersivity. For User defined, use it to specify the dispersion components as
user-defined constants or expressions. Select Isotropic, Diagonal, Symmetric, or
Anisotropic based on the properties of the dispersion tensor.

Select Dispersivity when Convection has been added as the transport mechanism. Specify
the dispersivities (SI unit: m) to define the dispersion tensor DD (SI unit: m2/s)
together with the velocity field u. Select an option from the Dispersivity model list:
Isotropic (the default) or Transverse isotropic based on the properties of the porous
media. For isotropic porous media, specify the longitudinal and transverse
dispersivities. For transverse isotropic porous media, specify the longitudinal,
horizontal transverse, and vertical transverse dispersivities.

Adsorption
Use this node to model adsorption of the fluid phase species onto the porous media
surface. It is available as a subnode to the Porous Media Transport Properties and the
Partially Saturated Porous Media nodes.

This feature is only available in a limited set of add-on products. See

http://www.comsol.com/products/specifications/ for more details on
availability.

MATRIX PROPERTIES
Use the Porous material list to define a material specifying the matrix properties on the
current selection. By default the Domain material is used.

The density of the porous media is needed when modeling adsorption to the surface
of the porous matrix. By default Density ρ is defined from the domain material.

ADSORPTION
Select a Sorption type — Langmuir (the default), Freundlich, or User defined to specify
how to compute cP, the amount of species sorbed to the solid phase (moles per unit
dry weight of the solid):

• For Langmuir:

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 173

 KL c ∂c P K L c Pmax
c P = c Pmax -------------------- -------- = ---------------------------
-
1 + KL c ∂c ( 1 + KL c )
2

Enter a Langmuir constant kL,c (SI unit: m3/mol) and an Adsorption maximum
cp,max,c (SI unit: mol/kg):

• For Freundlich:

c N ∂c P cP
c P = K F  -------- -------- = N -----
- Freundlich
 c ref ∂c c

Enter a Freundlich constant kF,c (SI unit: mol/kg), a Freundlich exponent NF,c
(dimensionless), and a Reference concentration cref,c (SI unit: mol/m3).

• For User defined:

∂c P
c P = KP c -------- = K P User defined
∂c

Enter an Adsorption isotherm kP,c (SI unit: m3/kg).

For more information, see Adsorption in the theory section.

FURTHER READING
See the theory chapter in the section Transport of Diluted Species in Porous Media.

Partially Saturated Porous Media

Use this node to model the concentration of diluted species transported by a liquid
through in partially filled porous media. The interstices of the porous media contains
the liquid carrier phase and gas pockets. A part from convection and diffusion, the
node contains functionality to include species evolution through adsorption,
dispersion, reaction, and volatilization.

This feature is only available in a limited set of add-on products. See

http://www.comsol.com/products/specifications/ for more details on
availability.

174 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

MODEL INPUTS
The temperature model input is always available. Select the source of the Temperature.
For User defined, enter a value or expression for the temperature in the input field. This
input option is always available.

You can also select the temperature solved for by a Heat Transfer interface added to
the model component. These physics interfaces are available for selection in the
Temperature list.

MATRIX PROPERTIES
Use the Porous material list to define a material specifying the matrix properties on the
current selection. By default the Domain material is used.

Specify the Porosity, εp (dimensionless) of the porous matrix. This is by default taken
From material. Select User defined to instead enter a different value.

SATURATION
Select Saturation or Liquid volume fraction from the list.

For Saturation, enter a value for s (dimensionless) between 0 and 1. The liquid volume
fraction is then computed from the saturation and porosity as θ = sεp.

For Liquid volume fraction, enter a value for θ (dimensionless) between 0 and the value
of porosity. The saturation is then computed from the porosity and the liquid volume
fraction as s = θεp.

Select a Fluid fraction time change: Fluid fraction constant in time (the default), Time
change in fluid fraction, or Time change in pressure head.

• For Time change in fluid fraction, enter dθ/dt (SI unit: 1/s).
• For Time change in pressure head, enter dHp/dt (SI unit: m/s) and a Specific
moisture capacity Cm (SI unit: 1/m).

CONVECTION
If transport by convection is active, the velocity field of the solvent needs to be
specified. Select the source of the Velocity field. For User defined, enter values or
expressions for the velocity components in the input fields. This input option is always
available.

You can also select the velocity field solved for by a Fluid Flow interface added to the
model component. These physics interfaces are available for selection in the Velocity
field list.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 175

 DIFFUSION
Select a Liquid material from the list.

Specify the Liquid diffusion coefficient DL,c (SI unit: m2/s). Enter a value or expression
for each of the species in the corresponding input field. The default is 1·10-9 m2/s.

Select the Effective diffusivity model, liquid: Millington and Quirk model (the default),
Bruggeman model, Tortuosity model, or User defined. For Tortuosity model, enter a value
for τL,c (dimensionless). The default is 1.

When the Volatilization in partially saturated porous media check box is selected on the
Settings window for the physics interface, also define the Gas material, Gas diffusion
coefficient, and Effective diffusivity model, gas.

MIGRATION IN ELECTRIC FIELD

This section is available when the Migration in electric field check box is selected. It is
similar to that in Porous Media Transport Properties feature. Select the source of electric
field from the Electric potential list. The default selection to Mobility is the
Nernst-Einstein relation.

DISPERSION
This section is available when the Dispersion in porous media check box is selected on
the Settings window for the physics interface. The settings are the same as for Porous
Media Transport Properties.

VOLATILIZATION
This section is available when the Volatilization in partially saturated porous media check
box is selected on the Settings window for the physics interface.

Enter a value for the Volatilization kG,c (dimensionless) for each species.

Volatilization
This feature is available when the Volatilization in partially saturated porous media check
box is selected on the Settings window for the physics interface.

Use this feature to model mass transfer at the boundary due to volatilization. The
feature can be added on boundaries of a Partially Saturated Porous Media domain. In
this case the porous media contains a liquid phase and a gas phase. The species
dissolved in the liquid are assumed to be vaporized at the boundary, and transported

176 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

into the surrounding bulk region due to convection and diffusion. The mass transfer
at the boundary is defined as

– n ⋅ J c = – h c ( k G,c c – c Gatm,c )

where hc is the mass transfer coefficient, kG,c the volatilization coefficient, and cGatm,c
the concentration in the surrounding atmosphere.

This feature is only available in a limited set of add-on products. See

http://www.comsol.com/products/specifications/ for more details on
availability.

VOLATILIZATION
Enter a Mass transfer coefficient hc defining the transfer into the surrounding media.
This can be given by boundary layer theory. When assuming that no convective flow
is present in the surrounding, the mass transfer coefficient can be defined from the gas
diffusion coefficient DGc and the thickness of the diffusion layer ds in the manner of

D Gc
h c = ----------
ds

Also give the atmospheric concentration for each species, cGatm,c. The Volatilization
coefficient kG,c for each species are taken from the adjacent Partially Saturated Porous
Media domain.

Reactive Pellet Bed

Use this feature to model packed bed reactors with catalytic pellets. For details, see the
section Theory for the Reactive Pellet Bed. By default, subnodes for Reactions and are
added.

This feature is only available in a limited set of add-on products. See

http://www.comsol.com/products/specifications/ for more details on
availability.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 177

 BED PARAMETERS
Here you can specify the bed porosity, which is the void fraction in the packed bed
structure. Select From densities to calculate the porosity from the bed density and the
individual pellet density. Select User defined to specify the porosity directly.

PELLET SHAPE AND SIZE

The default shape is spherical. Cylinders, flakes, and user-defined shapes can also be
selected. A uniform pellet size or a discrete size distribution can be selected. Select a
Pellet size distribution — Uniform size (the default), Two sizes, Three sizes, Four sizes, or
Five sizes to select up to five different particle sizes.

Depending on the shape selection, equivalent radii or volumes and surface areas will
be required as input. If a size distribution is selected, the volume percentage of each
size is required as input.

Note that different chemical reactions can be specified for each pellet size if a
distribution is specified.

SURFACE SPECIES
In order to add surface species, click the Add button and enter the species name in the
Surface species table. Added surface species are be available inside all pellet types
defined in the Pellet Shape and Size section, but not in the bulk fluid.

For each pellet type, specify the Reactive specific surface area, Sb,reac (SI unit: 1/m),
corresponding to the surface area, per volume, available for surface reactions.

PELLET PARAMETERS
Enter a Pellet porosity εpe (dimensionless) to specify the porosity of the pellet internals.

Select Diffusion model — Millington and Quirk model (the default), Bruggeman model,
Tortuosity model, or User defined to describe the effective correction of the diffusion
coefficient in the pellet. In the case of the Tortuosity model, a value for the tortuosity
τpe within the pellet is required.
Enter also the Diffusion coefficient Dpe,c (SI unit: m2/s). If a User defined diffusion
model is selected, an Effective diffusion coefficient Dpeff,c (SI unit: m2/s) is entered. The
default value is 1·10-9 m2/s in both cases.

178 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

PELLET-FLUID SURFACE
For the coupling of concentration between the pellet internals and the surrounding
fluid, two Coupling type options are available:

• Continuous concentration, assuming that all resistance to mass transfer to/from the
pellet is within the pellet and no resistance to pellet-fluid mass transfer is on the bulk
fluid side. The concentration in the fluid will thus be equal to that in the pellet pore
just at the pellet surface: c pe,i = c i . This constraint also automatically ensures flux
continuity between the internal pellet domain and the free fluid domain through
so-called reaction forces in the finite element formulation.
• Film resistance (mass flux): The flux of mass across the pellet-fluid interface into the
pellet is possibly rate determined on the bulk fluid side, by film resistance. The
resistance is expressed in terms of a film mass transfer coefficient, hDi, such that:
N i,inward = h D, i ( c i – c pe, i ) .

The Film resistance (mass flux) option computes the inward surface flux,
Ni,inward=hDi(ci-cpe,i). hDi is the mass transfer coefficient (SI unit: m/s) and is
calculated with the default Automatic setting from a dimensionless Sherwood number
expression or with User defined mass transfer coefficients.

The Active specific surface area (SI unit: m-1) is required to couple the mass transfer
between the pellets and the bed fluid. Select either the Automatic setting that calculates
the specific surface area from the shape information given above. User defined is also
available for explicit surface area specification.

The Sherwood number expression can be computed from three available expressions:
Frössling, Rosner, and Garner and Keey. The Frössling equation is the default and
probably the most commonly used for packed spheres. All of these are based on the
dimensionless Reynolds, Re, and Schmidt, Sc, numbers, which are computed from
Density and Dynamic viscosity. Select these to be taken either From material or choose
the User defined alternative.

PELLET DISCRETIZATION
The extra dimension in the pellet needs to be discretized into elements. Select a
Distribution — Cubic root sequence (the default), Linear, or Square root sequence. Enter
the Number of elements Nelem.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 179

 CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.
See the details about the different constraint settings in the section Constraint
Reaction Terms in the COMSOL Multiphysics Reference Manual.

FURTHER READING
Theory for the Reactive Pellet Bed in the Theory section of this manual.

For an application using the Reactive Pellet Bed feature, see

• A Multiscale 3D Packed Bed Reactor: Application Library path

Chemical_Reaction_Engineering_Module/Reactors_with_Porous_Catalysts/
packed_bed_reactor_3d
Web link: http://www.comsol.com/model/
a-multiscale-3d-packed-bed-reactor-17019

Reactions
The Reactions subfeature to the Reactive Pellet Bed is used to define reaction terms to
the transport within the reactive pellets. The feature also defines the corresponding
averaged heat sources to be applied to heat transport in the bulk fluid.

DOMAIN SELECTION
From the Selection list, choose the domains on which to define rate expression or
expressions that govern source terms in the transport equations.

Several reaction nodes can be used to account for different reactions in different parts
for the modeling geometry.

REACTION RATES
Add a rate expression Ri (SI unit: mol/(m3·s)) for species i using a value or an
expression. One reaction rate per species and pellet type can be entered.

Note that if you have the Chemistry interface available, provided with the Chemical
Reaction Engineering Module, the reaction rate expressions can be automatically
generated and picked up using the drop-down menu. For an example, see the
application Fine Chemical Production in a Plate Reactor.

180 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

SURFACE REACTION RATES
The section is available when one or more surface species have been added in the
Surface Species section of the Reactive Pellet Bed feature.

Specify the rate expression Rsurf,i (SI unit: mol/(m2·s)) corresponding to the surface
reaction rate of each volumetric species i participating in the surface reaction.
Furthermore, specify the surface reaction rates for the participating surface species in
the corresponding table.

If several pellet types have been defined, one set of surface reaction rates per pellet type
can be defined.

Note that if you have the Chemistry interface available, provided with the Chemical
Reaction Engineering Module, the reaction rate expressions can be automatically
generated and picked up using the drop-down menu.

HEAT SOURCE
Specify the heat source originating from the heat of reaction of the chemical reactions
inside the pellet can be specified. Both heat sources from reactions in the fluid, and
heat sources resulting from surface reactions can be defined. When using several pellet
types, heat sources for each type can be added.

The heat sources are most conveniently picked up from a Chemistry feature that
defines the reaction rate and the heat of reactions. In that case, the Rate expression can
be selected from the drop-down menu. Else it can be set to User Defined.

The defined heat source can be used by a Heat Source feature in any of the heat
transfer interfaces.

Species Source
In order to account for consumption or production of species in porous domains, the
Species Source node adds source terms expressions Si to the right-hand side of the
species transport equations.

DOMAIN SELECTION
From the Selection list, choose the domains on which to define rate expression or
expressions that govern the source term in the transport equations.

If there are several types of domains, with subsequent and different reactions occurring
within them, it might be necessary to remove some domains from the selection. These
are then defined in an additional Species Source node.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 181

 SPECIES SOURCE
Add a source term Si (SI unit: mol/(m3·s)) for each of the species solved for. Enter a
value or expression in the field of the corresponding species.

Hygroscopic Swelling
The Hygroscopic Swelling multiphysics coupling node ( ) is used for moisture
concentration coupling between the Solid Mechanics interface and either the
Transport of Diluted Species or Transport of Diluted Species in Porous Media
interfaces.

Hygroscopic swelling is an effect of internal strain caused by changes in moisture

content. This strain can be written as

ε hs = β h M m ( c mo – c mo,ref )

where βh is the coefficient of hygroscopic swelling, Mm is the molar mass, cmo is the
moisture concentration, and cmo,ref is the strain-free reference concentration.

It requires a license of either the MEMS Module or the Structural Mechanics Module.
The multiphysics feature will appear automatically if both the Transport of Diluted
Species and the Solid Mechanics interfaces are added to the same component. For the
most current information about licensing, please see See http://www.comsol.com/
products/specifications/.

FURTHER READING
More information about how to use hygroscopic swelling can be found in Hygroscopic
Swelling Coupling section in the Structural Mechanics Module User’s Guide.

More information about multiphysics coupling nodes can be found in the section The
Multiphysics Branch in the COMSOL Multiphysics Reference Manual.

182 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Fracture
Use this node to model mass transport along thin fractures in porous media. The node
assumes that the transport in the tangential direction along the fracture is dominant,
as a result of lower flow resistance.

This feature is only available in a limited set of add-on products. See

http://www.comsol.com/products/specifications/ for more details on
availability.

FRACTURE PROPERTIES
Specify a value for the Fracture thickness dfr.

MATRIX PROPERTIES
Use the Porous material list to define a material specifying the matrix properties on the
current selection. By default the Boundary material is used.

Specify the Porosity, εp (dimensionless) of the porous matrix. This is by default taken
From material. Select User defined to instead enter a different value.

CONVECTION
Select an option from the Velocity field list to specify the convective velocity along the
fracture. For a consistent model, use a Fracture Flow feature in a Darcy’s Law interface
to compute the fluid flow velocity in the fracture.

For User defined, enter values or expressions for the velocity components in the table
shown.

The settings for the Diffusion, and Dispersion sections are the same as for
Porous Media Transport Properties.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 183

 The Chemistry Interface
The Chemistry (chem) interface ( ) is found under the Chemical Species Transport
branch ( ) when adding a physics interface.

This physics interface is a tool for generating a set of variables to be used for modeling
chemical species and reactions systems. The variables are generated from species and
reaction properties and can be divided in two categories:

• Rate expressions and heat sources for use in mass and heat balances
• Material property variables (mixture density, diffusivities, viscosity, etc.) for use in
space-dependent transport equations.
Many of the fields and nodes described in this section are only made available when
either a Reaction or a Species (or both) subnode is added to the Model Builder. All
predefined constants and expressions can be overwritten by user-defined expressions.
This makes it possible to go beyond the modeling assumptions set as defaults in this
physics interface.

The following is a description of the features and fields available on the Settings
window for the Chemistry interface.

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is chem.

MODEL INPUTS
This section sets the Temperature and Pressure. In the lists, it is possible to edit the User
defined option to the temperature and pressure from interfaces available in the Model
Builder. The latter choice couples the interfaces.

184 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

SPECIES MATCHING
Use the table in this section to specify the concentrations for the variables generated
by the Reaction and the Species features (the reaction rate for example), and to define
mixture properties (transport and thermodynamic properties).

Select Diluted Species in the Mixture type list to use the concentration variables from a
Transport of Diluted Species interface. The same setting should be used for any other
interface solving for species concentrations using a diluted species assumption. Enter
the names of the dependent variables in the Molar concentration column.

Select Concentrated Species in the Mixture type list in order to use the mass fractions
from a Transport of Concentrated Species interface. Enter the names of the dependent
variables in the Mass fraction column.

The name of the reaction rate variables generated by the interface can be seen in the
Reaction Rate column of the table. The syntax of the reaction rate variables depend on
the Species type selected in the Species Settings window. Bulk species and Solvent use
the syntax R_speciesname, while Surface species uses R_speciesname_surf.
Selecting Concentrated species for the Mixture type, the base of syntax for the reaction
rate is changed. to Rw_speciesname.

EXTRA DIMENSION
Select Define variables in extra dimension when the current Chemistry interface is
coupled to a feature on an extra dimension. An example of this is when the
concentrations in the Concentration input column of the Model Inputs, Concentration
corresponds to pellet concentrations from a Reactive Pellet Bed feature in a Transport
of Diluted Species interface.

When selected, generated variables will be defined using concentrations averaged over
the extra dimension. Note that the generated variables are global in order be available
on the main geometry, in contrast to variables on the extra dimension which only exist
on the corresponding dimension.

MIXTURE
Select a Mixture to specify the phase, Gas or Liquid, of the reaction fluid.

THE CHEMISTRY INTERFACE | 185

 Mixture Density
Mixture density always has two settings available: Automatic or User defined. The density
is compiled for both multicomponent and solute-solvent solutions.

• Automatic (ideal liquid) selected for Liquid, considers the liquid as ideal and
incompressible. The liquid mixture density depends on the density of i number of
pure species (ρi) and the species weight fraction (wi).
1
ρ = --------------
wi
 ------
ρi
i

The volume fraction is given by the species concentration (ci) and the molar mass
(Mi).
ci Mi
w i = --------------------
 ci Mi
i

• Automatic set for Gas calculates the gas mixture density (ρ) from the concentrations
(ci) and molar masses (Mi) of the mixture species, which are automatically taken
from Species features.

ρ =  ci Mi (4-1)
i

• If a Species Type is set to Solvent and the Mixture is Liquid, the mixture density is the
same as the solvent density as defined in Density in General parameters in the Species
node. When Mixture is Gas, the mixture density is calculated from Equation 4-1 only
for the species set as Solvent.

ACTIVITY
Select the Use activity check box to solve for species activities instead of species
concentrations, which is a common approach when non-ideal fluids are modeled.

An activity coefficient other than 1 can be set for each species for the Species node in
the Species Concentration/Activity section.

CALCULATE THERMODYNAMIC PROPERTIES

Select the Calculate thermodynamic properties check box to enable the interface to
compute thermodynamic properties, especially critical if the reaction kinetics are
defined at nonisothermal conditions.

186 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Feature Nodes Available for the Chemistry Interface
The following feature nodes are available from the Chemistry ribbon toolbar (Windows
users), Chemistry context menu (Mac or Linux users), or right-click to access the
context menu (all users).

• Equilibrium Reaction Group • Species

• Reaction • Species Activity
• Reaction Thermodynamics1 • Species Group
• Reversible Reaction Group • Species Thermodynamics1
1
This is a subnode and it is only available together with a parent node.

Reaction
To add a Reaction node ( ) either right-click the Chemistry node or on the Chemistry
toolbar click Reaction.

REACTION FORMULA

Formula
Enter a chemical reaction Formula. Click Apply to make the interface examine the
species taking part in the model’s reactions and automatically add the associated
Species features to the Model Builder.

Reaction Type
Select the Reaction type — Reversible, Irreversible, or Equilibrium — or edit the
expression directly in the Formula field. In the latter case, specify the reaction type with
a delimiter separating the two sides of the equation:

• <=> denotes a Reversible reaction

• => denotes an Irreversible reaction
• = denotes a reaction at chemical Equilibrium

Each Reaction type has its own set of reaction kinetics:

• If the reaction is Reversible or Irreversible, the reaction rate for a species is:
Ri = νi r (4-2)

THE CHEMISTRY INTERFACE | 187

 • If the reaction is at Equilibrium, the equilibrium expression is equal to the
equilibrium constant:
K eq = K eq0

REACTION RATE
This section is available when the Reaction type is either Reversible or Irreversible.

The Automatic Reaction rate expression is set up according to the mass action law:

• For an Irreversible reaction type, the reaction rate becomes:

f – ν ij
rj = kj ∏ ci
i ∈ react

• For a Reversible reaction type, the expression instead becomes:

f – ν ij νij
∏
r
rj = kj ci – kj ∏ ci (4-3)
i ∈ react i ∈ prod

RATE CONSTANTS
This section applies for Reversible or Irreversible reactions and defines the reaction rate
constants used in the reaction rates.

Forward Rate Constant and Reverse Rate Constant

The Forward rate constant kf is used for both Reversible and Irreversible reactions. The
Reverse rate constant kr is only used for Reversible reactions (Equation 4-3).

The SI units of the rate constants are automatically based on the order of the reaction
with respect to the concentrations, as defined in the Reaction formula.

Specify Equilibrium Constant

The Specify equilibrium constant check box is available for Reversible reactions. If the
check box is selected the rate constants are defined in a different manner with the
reverse rate constant being computed from the following expression:

r f
k = k ⁄ K eq0

Thus, in this case, the forward rate constant and equilibrium constant for the reaction
are needed. The Equilibrium constant is edited in the Equilibrium Settings section.

188 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Use Arrhenius Expressions
When the Use Arrhenius expressions check box is selected the Arrhenius parameters are
automatically used in predefined expressions for the forward and reverse rate constants
kfand kr, respectively.
f
f f n f
k = A ( T ⁄ T ref ) exp ( – E ⁄ ( R g T ) )

f rf
r r n r
k = A ( T ⁄ T ref ) exp ( – E ⁄ ( R g T ) )

Specify the activation energy and the frequency factor in the Arrhenius expressions to
account for temperature variations. The reference temperature, Tref equals 1 K. The
available fields are based on the Reaction type chosen in the Reaction node. Enter
values or expressions for each of the following (reverse expressions are only available
for reversible reactions):

• Forward frequency factor Af and Reverse frequency factor Ar (SI unit: (mβ/
mol)α − 1/s, where α equals the order of the reaction and β is 3 or 2 for volumetric
or surface reactions, respectively)
• Forward temperature exponent nf and Reverse temperature exponent nr
• Forward activation energy Ef and Reverse activation energy Er (SI unit: J/mol)

EQUILIBRIUM SETTINGS
This section is available for equilibrium reactions, and for reversible reactions when the
Specify equilibrium constant check box has been selected.

Equilibrium Expression
For an equilibrium reaction, specify the Equilibrium expression. When the Equilibrium
expression is set to Automatic the following expression is used:

νij
∏ ci
i ∈ prod
K eqj = ----------------------------
– ν ij
∏ ci
i ∈ react

Select User defined from the Equilibrium expression list to instead enter a manually
defined equilibrium expression.

THE CHEMISTRY INTERFACE | 189

 Equilibrium Constant
Specify the Equilibrium constant Keq0 for an equilibrium reaction, or for a reversible
reaction when the Specify equilibrium constant check box has been selected (in the Rate
Constants section).

The Equilibrium constant can either be User defined, or automatically defined when set
to Automatic or Thermodynamics.

Use the Automatic option to compute the equilibrium constant for an ideal system.
This settings requires that the Calculate thermodynamic properties in the corresponding
section is selected.

The Thermodynamics option is available when all reactions in the interface are
equilibrium reactions, and the interface is fully coupled to a Thermodynamic System
(see Species Matching). Use this setting to automatically compute the equilibrium
constant for an ideal or non-ideal system, dependent on the thermodynamic model
applied for the coupled system.

Using Automatic or Thermodynamics, Keq0 is calculated from the Gibbs free energy of
the reaction. For more details see The Equilibrium Constant and the Automatically
Defined Equilibrium Constants section therein.

REACTION THERMODYNAMIC PROPERTIES

This section has information about thermodynamic properties that relate to a selected
reaction and is available when the Calculate Thermodynamic Properties check box is
selected for the Chemistry interface. Several Automatic definitions are available here.

Enthalpy of Reaction
The Enthalpy of reaction H (SI unit: J/mol) is calculated by the interface from species
properties and the related stoichiometric coefficients:

Hj =  ν ij h i –  ( – ν ij )h i (4-4)
i ∈ prod i ∈ react

Entropy of Reaction
The Entropy of reaction S (SI unit: J/(mol·K)) comes from a similar expression:

Sj =  ν ij s i –  ( – ν ij )s i (4-5)
i ∈ prod i ∈ react

In Equation 4-4 and Equation 4-5, hi and si are the species’ molar enthalpy and molar
entropy, respectively.

190 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Enter these quantities in the Species Thermodynamic Expressions section for the Species
node either by using the predefined polynomial or by providing a custom expression
or constants.

The stoichiometric coefficients, vij, are defined as being negative for reactants and
positive for products. Using Equation 4-4 and Equation 4-5 to equate the Gibbs free
energy of reaction enables the equilibrium constant to be expressed according to
Equation 4-4.

Heat Source of Reaction

The Heat source of reaction (SI unit: W/m3) is automatically computed from the heat
of each reaction j, given by:

Qj = –Hj rj

Using the Reaction Node

Species
When a Reaction is defined, a Species node ( ) is automatically generated for the
participating reactants and products. This feature enables you to review and enter
species specific information regarding chemical kinetics, thermodynamics and
transport properties.

It is also possible to add and define an individual Species node: on the Chemistry toolbar
click Species or right-click the Chemistry node and select it from the context menu.

SPECIES NAME
When a Species node is automatically generated using the Formula text field for the
Reaction node, the Species name is also automatically generated.

For a Species node added individually, enter a Species name in the field and click Apply.

Creating Valid Species Names and Labeling

SPECIES TYPE
Select a Species type—Bulk species, Surface species, or Solvent.

THE CHEMISTRY INTERFACE | 191

 Bulk species and Solvent are solved for volumetric concentrations (SI unit: mol/m3),
while Surface species are solved for surface concentration (SI unit: mol/m2). The
compositions for Bulk species and Solvent use the syntax c_speciesname, while Surface
species uses csurf_speciesname_surf.

When Surface species is selected, the corresponding reaction formula introduces (ads)
after the species notation and changes the species’ name to speciesname_surf.
Additionally, the Species node name is updated in a similar fashion.

GENERAL PARAMETERS
The General Parameters section deals with species parameters.

Edit, if necessary, the species Molar mass M and the ionic Charge z of the species in
question.

It is possible to specify the species density ρ when the fluid Mixture is specified as Liquid.
The default value is that of water at 293 K.

REACTION RATE
Change the Automatic default setting to User defined to use a species reaction rate other
than the one set up in the associated Reaction node. For individual species, use the User
defined option to set a reaction rate other than zero (that is, non-reactive).

Edit either the Rate expression (SI unit: mol/(m3·s)), the Surface rate expression (SI
unit: mol/(m2·s)), or both. For a bulk species, both expressions appear if surface
reactions are present in the reactor since the reaction of the species can depend both
on bulk reaction R and surface reaction Rads rates. For a surface species, only the
surface reaction rate Rads appears.

ADDITIONAL SOURCE
The Additional Source section is available in order to include additional rate
contribution for the species to the reaction kinetics. When the Additional source check
box is selected, add an Additional rate expression in the text field (SI unit: mol/m3).

SPECIES CONCENTRATION/ACTIVITY
To account for non-ideality in the fluid mixture adjust the activity coefficient in the
Activity coefficient text field here. The section is only shown if activity instead of
concentration has been chosen in the interface, i.e. the Use activities check box is
selected on the Chemistry interface Settings window

192 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Click to select the Locked concentration/activity check box if the species concentration
or activity should be treated as constant.

SPECIES THERMODYNAMIC EXPRESSIONS

The parameters utilized for calculation of thermodynamic mixture and reaction
properties are set in this section. It is accessed when the Calculate Thermodynamic
Properties check box is selected on the Chemistry interface Settings window, that is,
temperature dependence is accounted for.

Choose the User defined alternative to specify Cp, h, and s directly.

Reversible Reaction Group

The Reversible Reaction Group node ( ) allows input of a large number of reversible
reactions in the same table. All reactions are treated in the same way. More than one
Reversible Reaction Group can be added to a component.

Add the node from the Chemistry toolbar or right-click Chemistry and add it from the
context menu.

For the case when reaction kinetics data are entered manually into the Reaction table
and temperature dependent reaction kinetics apply (Calculate Thermodynamic
Properties check box is selected), right-click to add a Reaction Thermodynamics
subnode or select it from the Chemistry toolbar, Attributes menu. In it, the Enthalpy of
Reaction (J/mol) for each reaction can be specified.

REACTION TABLE
The reversible reactions in the Reaction table are numbered and contain reactants,
products, and kinetic parameters describing the reaction. Use the buttons under the
Reaction table to add and sort the reaction details.

• In general, use the Move Up ( ), Move Down ( ), and Delete ( ) buttons and
the fields under tables to edit the table contents. Or right-click a table cell and select
Move Up, Move Down, or Delete.
• The Add button ( ) adds default reactant, A, and product, B, with a default. Click
the corresponding field to edit the reactant, product, or parameters. After editing
the Species Group node is also updated. It is created together with the reaction
group.
• You can save the parameters to a text file to reuse in other models. Click the Save to
File button ( ) and enter a File name in the Save to File dialog box, including the

THE CHEMISTRY INTERFACE | 193

 extension.txt. Click Save to store the parameters in a text file or in a Microsoft Excel
Workbook spreadsheet if the license includes LiveLink™ for Excel®. The information
is saved in space-separated columns in the same order as displayed on screen. When
saving to Excel, an Excel Save dialog box appears where you can specify the sheet and
range and whether to overwrite existing data, include a header, or use a separate
column for units.
• You can import or load data in files from a spreadsheet program, for example, with
the Load from File button ( ) and the Load from File dialog box that appears. Data
must be separated by spaces or tabs. If there is already data in the table, imported
parameters are added after the last row. Move or edit rows as needed. If the license
includes LiveLink™ for Excel® you can also load parameters from a Microsoft Excel
Workbook spreadsheet. Then an Excel Load dialog box appears where you can specify
the sheet and range and whether to overwrite existing data. It is also possible to
import from a spreadsheet containing a separate column for units.

In the case of twenty or more reactions the Disable updating variables during editing
table check box is available. Select this to speed up editing text fields; automatic
updates related to edits do not occur until you click to clear the check box.

CREATE REACTION AND SPECIES

Enter a reaction number in the Moving reaction (with the number) from table text field
and click Create Reaction to remove the reaction from the Reaction table to the model
tree. This introduces a reaction node named after the reaction number and species
names and simultaneously creates corresponding species nodes. This action is
powerful, since it enables all the editing possibilities available for Reaction and Species
nodes.

Equilibrium Reaction Group

The Equilibrium Reaction Group node ( ) allows for input of a large number of
equilibrium reactions in the same table. This node functions in the same way as the
Reversible Reaction Group for reversible reactions.

Add the node from the Chemistry toolbar or right-click Chemistry and add it from the
context menu.

For the case when reaction kinetics data are entered manually into the Reaction table
and temperature dependent reaction kinetics apply (Calculate Thermodynamic
Properties check box is selected), right-click to add a Reaction Thermodynamics

194 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

subnode or select it from the Chemistry toolbar, Attributes menu. In it, the Enthalpy of
Reaction (J/mol) for each reaction can be specified.

REACTION TABLE
The equilibrium reactions in the Reaction table are numbered and contain reactants,
products, and kinetic parameters describing the reaction. Use the buttons under the
Reaction table to add and sort the reaction details.

• In general, use the Move Up ( ), Move Down ( ), and Delete ( ) buttons and
the fields under tables to edit the table contents. Or right-click a table cell and select
Move Up, Move Down, or Delete.
• The Add button ( ) adds default reactant, A, and product, B, with a default. Click
the corresponding field to edit the reactant, product, or parameters. After editing
the Species Group node is also updated. It is created together with the reaction
group.
• You can save the parameters to a text file to reuse in other models. Click the Save to
File button ( ) and enter a File name in the Save to File dialog box, including the
extension.txt. Click Save to store the parameters in a text file or in a Microsoft Excel
Workbook spreadsheet if the license includes LiveLink™ for Excel®. The information
is saved in space-separated columns in the same order as displayed on screen. When
saving to Excel, an Excel Save dialog box appears where you can specify the sheet and
range and whether to overwrite existing data, include a header, or use a separate
column for units.
• You can import or load data in files from a spreadsheet program, for example, with
the Load from File button ( ) and the Load from File dialog box that appears. Data
must be separated by spaces or tabs. If there is already data in the table, imported
parameters are added after the last row. Move or edit rows as needed. If the license
includes LiveLink™ for Excel® you can also load parameters from a Microsoft Excel
Workbook spreadsheet. Then an Excel Load dialog box appears where you can specify
the sheet and range and whether to overwrite existing data. It is also possible to
import from a spreadsheet containing a separate column for units.

In the case of twenty or more reactions the Disable updating variables during editing
table check box is available. Select this to speed up editing text fields; automatic
updates related to edits do not occur until you click to clear the check box.

THE CHEMISTRY INTERFACE | 195

 Species Group
The Species Group node ( ) contains information on a molecular level about the
volumetric species and the surface species present in the model. The Property for
Volumetric Species or Property for Surface Species tables typically collect parameters
from when importing CHEMKIN transport files.

Add the node from the Chemistry toolbar or right-click Chemistry and add it from the
context menu. This node is also automatically added when either the Reversible
Reaction Group or the Equilibrium Reaction Group are used.

For the case of temperature dependent reaction kinetics (Calculate Thermodynamic

Properties check box is selected), a Species Thermodynamics subnode is automatically
created in which the thermodynamic properties of the species can be specified.

Reaction Thermodynamics
The Reaction Thermodynamics subnode ( ), the Enthalpy of Reaction (J/mol) of
each reaction can be specified. This node overrides all the automatically calculated
reaction enthalpies as defined in the Species Thermodynamics subnode.

Add the Reaction Thermodynamics node from the Chemistry toolbar, Attributes menu.
Alternatively, when the Calculate Thermodynamic Properties check box is selected on
the Chemistry interface Settings window, right-click a Reversible Reaction Group or
Equilibrium Reaction Group to add the Reaction Thermodynamics subnode.

Species Activity
The Species Activity node ( ) creates variables for the activities of all the species/
surface species present in the Species Group parent feature. Edit the Activity coefficient
field in the Species Activity or Surface Species Activity tables by clicking in these.

Species Activity is a subnode to the Species Group node. It is automatically generated

when non-ideality in the fluid mixture is accounted for; when the Use activity check
box is selected in the Activity section.

Species Thermodynamics
The Species Thermodynamics node ( ) creates variables for the enthalpies, entropies,
and heat capacities for all the species/surface species present in the Species Group

196 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

parent feature. The purpose is to compute thermodynamic mixture properties and the
heat of reactions.

This node is a subnode to the Species Group node when the Calculate
Thermodynamic Properties check box is selected on the Chemistry interface Settings
window.

THE CHEMISTRY INTERFACE | 197

 T he N e r ns t - P la n c k- Poi sson E q u at i on s
Interface
The Nernst-Planck-Poisson Equations interface ( ), found under the Chemical Species
Transport branch ( ) when adding a physics interface, is a predefined multiphysics
interface for modeling transport of electrolyte species without the otherwise common
assumption of local electroneutrality. This allows for simulating charge separation that
typically arises close to an electrode surface, where ions in the electrolyte are attracted
and repelled by unscreened excess charge on the electrode. The charge separation
region, also called the diffuse double layer, normally extends a few nanometers away
from the electrode surface into the electrolyte. The study of the charge separation 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.

The Nernst-Planck-Poisson Equations predefined multiphysics interface adds The

Transport of Diluted Species Interface ( ) (with Migration enabled), which solves
for the Nernst-Planck equations without charge neutrality, and The Electrostatics
Interface( ), that solves for the Poisson’s equation.

A Space Charge Density Coupling ( ) multiphysics node is also added. This node
computes the local space charge, based on the local concentrations and species charges
in the Transport of Diluted Species interface, and adds it to Poisson’s Equation in the
Electrostatics interface.

198 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Finally, a Potential Coupling ( ) multiphysics node is added that applies the
potential dependent variable in the Electrostatics interface into the migration term of
the Transport of Diluted Species interface.

• The Multiphysics Branch in the COMSOL Multiphysics

Reference Manual.
• The Transport of Diluted Species Interface.
• The Electrostatics Interface
• Space Charge Density Coupling
• Potential Coupling

Diffuse Double Layer: Application Library path

Electrochemistry_Module/Tutorials/diffuse_double_layer

THE NERNST-PLANCK-POISSON EQUATIONS INTERFACE | 199

 The Electrophoretic Transport
Interface
The Electrophoretic Transport (el) interface ( ), found under the Chemical Species
Transport branch ( ), is used to solve for the electrophoretic transport of an
arbitrarily number of species in water-based system, subject to potential gradients. The
species transported can be any combination of weak and strong acids and bases,
ampholytes and uncharged species. The transport of masses and charge is based on the
Nernst-Planck equations for molecular transport, in combination with
electroneutrality, dissociation equilibria for weak acids, bases and ampholytes as well as
the water auto-ionization reaction.

The physics interface can simulate most forms of electrophoresis modes, such as zone
electrophoresis, isothachophoresis, isoelectric focusing and moving boundary
electrophoresis.

Gel electrophoresis can be simulated by the inclusion of immobile charged species.

The interface supports simulation in 1D, 2D, and 3D as well as for axisymmetric
components in 1D and 2D.

The dependent variables are the electrolyte potential, and the molar concentrations of
the included species, added individual by each species node in the model tree.

Zone Electrophoresis: Application Library path Electrochemistry_Module/

Electrochemical_Engineering/zone_electrophoresis

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is el.

200 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

DOMAIN SELECTION
If any part of the model geometry should not partake in the mass transfer model,
remove that part from the selection list.

OUT-OF-PLANE THICKNESS

For 2D components, enter a value or expression for the out-of-plane

Thickness d (SI unit: m). The value of d determines the size of the domain
perpendicular to the modeled 2D cross section. This value yields, for
example, the correct total current when the current density is obtained
from a 2D simulation.

CROSS SECTIONAL AREA

For 1D components, enter a Cross sectional area Ac (SI unit: m2) to define
a parameter for the area of the geometry perpendicular to the 1D
component. The value of this parameter is used, among other things, to
automatically calculate the total current from the current density vector.
The analogy is valid for other fluxes. The default is 1 m2.

TRANSPORT MECHANISMS
Mass transport due to diffusion and migration is always included. Use the check boxes
available under Additional transport mechanisms to control other transport
mechanisms.

• By default, the Convection check box is selected. Clear the check box to disable
convective transport.
• The Mass transfer in porous media check box activates functionality specific to species
transport in porous media. When selected, the Porous Matrix Properties node can
be added to a domain to specify the electrolyte volume fraction and tortuosity, and
the Effective Transport Parameter Correction sections are enabled in the species
nodes.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 201

 CONSISTENT STABILIZATION
To display this sections, click the Show button ( ) and select Stabilization.

• When the Crosswind diffusion check box is selected, a weak term that reduces
spurious oscillations is added to the transport equation. The resulting equation
system is always nonlinear.
• For both Streamline diffusion and Crosswind diffusion, select an Equation residual.
Approximate residual is the default and means that derivatives of the diffusivity are
neglected. This setting is usually accurate enough and is computationally faster. If
required, select Full residual instead.

INCONSISTENT STABILIZATION
To display this section, click the Show button ( ) and select Stabilization. By default,
the Isotropic diffusion check box is not selected, because this type of stabilization adds
artificial diffusion and affects the accuracy of the original problem. However, this
option can be used to get a good initial guess for under-resolved problems.

ADVANCED SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.
Normally these settings do not need to be changed. Select a Convective term —
Nonconservative form (the default) or Conservative form. The conservative formulation
should be used for compressible flow.

DISCRETIZATION
The concentration variables are set to use Linear elements by default.

The potential variable is set to use Quadratic elements by default.

The Compute boundary fluxes check box is activated by default so that COMSOL
Multiphysics computes predefined accurate boundary flux variables. When this option
is checked, the solver computes variables storing accurate boundary fluxes from each
boundary into the adjacent domain.

If the check box is cleared, the COMSOL Multiphysics software instead computes the
flux variables from the dependent variables using extrapolation, which is less accurate
in postprocessing results but does not create extra dependent variables on the
boundaries for the fluxes.

202 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

The flux variables affected in the interface are:

• <name>.nIl, where <name> is the name of the interface (default is el), set on the
interface top node. This is the normal electrolyte current density.
• <name>.ntflux_<species_name> is the Species name (see Common Settings for
the Species nodes in the Electrophoretic Transport Interface below). This is the
normal total flux for each species.

Also the Apply smoothing to boundary fluxes check box is available if the previous check
box is checked. The smoothing can provide a more well-behaved flux value close to
singularities.

For details about the boundary fluxes settings, see Computing Accurate Fluxes in the
COMSOL Multiphysics Reference Manual.

Regarding the Value type when using splitting of complex variables, see Splitting
Complex-Valued Variables in the COMSOL Multiphysics Reference Manual.

DEPENDENT VARIABLES
The dependent variable name for the electrolyte potential variable is phil by default.

The name of the concentration dependent variables are named as el.xxx, where the el is
the name of the interface as set above, and the xxx string is controlled by the Species
name setting on the individual species nodes.

FURTHER READING

• Theory for the Electrophoretic Transport Interface

• Numerical Stabilization in the COMSOL Multiphysics Reference
Manual.
• In the COMSOL Multiphysics Reference Manual, see Table 2-3 for
links to common sections and Table 2-4 for common feature nodes.
You can also search for information: press F1 to open the Help window
or Ctrl+F1 to open the Documentation window.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 203

 Common Settings for the Species nodes in the Electrophoretic Transport
Interface
The interface features the following species nodes, applicable on the domain level:

• Ampholyte
• Fully Dissociated Species
• Uncharged Species
• Weak Acid
• Weak Base
Each species node add a dependent variable for the concentration. The initial and
boundary condition, as well as adding additional source reaction terms, for each
species concentration is controlled by adding subnodes to the species nodes:

• Concentration
• Flux
• Inflow
• Initial Concentration
• No Flux
• Outflow
• Species Source

The Ampholyte, Weak Acid and Weak Base are dissociation species and may define an
arbitrary number of dissociation steps. Each dissociation step is defined by it’s pKa (the
acid equilibrium constant) parameter. For the weak bases the pKa refers to the acid
constant of the conjugate acid. Each dissociation step adds one additional subspecies
concentration variable so that the concentration dependent variable represents the sum
of all subspecies, and initial and boundary conditions are defined with respect to this
total concentration.

All species node have a setting for the Species name, which needs to be unique. The
species name is used for naming of all related variables of the species. For species nodes
not defining any subspecies, the concentration variables are named as
<name>.c_<species_name> where <name> is the name of the interface (default is el),
set on the interface top node, and <species_name> is the Species name. For
dissociation species nodes defining multiple subspecies, the concentration nodes are
named as <name>.c<X>_<species_name> where <X> is the integer from 1 up to the

204 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

total number of subspecies. Note that the Solvent node automatically defines the
concentration variables for protons (<name>.cH) and hydroxide ions (<name>.cOH).

All species except the Uncharged Species carry charge and contribute to the total
electrolyte current which is used in the equation for solving the electrolyte potential.

The Immobile Species check box can be used to lock the concentration of a species, to,
for instance, define the immobile charges in a ion-selective membrane or a gel. When
the check box is enabled the concentration of the species is not added as a dependent
variable to the model; instead the concentration will be set to the value provided in the
Concentration field. The contribution to the electrolyte current for immobile species is
zero.

Diffusion and Migration Settings

All species, except when the Immobile Species check box has been enabled, may be
transported by diffusion, and charged species are also transported by migration in the
electric field.

For dissociation species you may choose to set the transport parameters to be the Same
for all species appearing in the different dissociation steps, or you may use Individual
settings for each subspecies.

Typically the mobilities and diffusivities for small species are related by the
Nernst-Einstein relation, and when this relation is enabled you can choose whether to
specify either the Diffusivity (SI unit: m2/s) or the Mobility (SI-unit: s·mol/kg). The
Debye-Hückel-Henry relation is commonly used for larger molecules, such as proteins.

Note: There are other definitions of the migration transport equations in literature
which use mobilities expressed in m2/(V·s), whereas COMSOL Multiphysics uses
s·mol/kg. To convert mobilities expressed in m2/(V·s) to the corresponding values in
s·mol/kg, you typically divide by the Faraday constant, F_const (96485 C/mol).

EFFECTIVE TRANSPORT PARAMETER CORRECTION

If Mass transfer in porous media is enabled on the interface top node, you may use the
settings of this section in the species nodes to account for the changed mass transport
in a porous domain due to the lowered porosity and the increased tortuosity.

The default correction model is Bruggeman, which multiplies the diffusivity and
mobility values by the porosity to the power of 1.5. The porosity of a domain is set by
the Porous Matrix Properties node.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 205

 IONIC STRENGTH CONTRIBUTION
To display this section, click the Show button ( ) and select Advanced Physics Options.

The Debye-Hückel-Henry relation makes use of the ionic strength for calculating the
species mobility from the diffusivity. All charged species contribute to the ionic
strength, either assuming the species contributing to an Ideal solution or by using the
Lindestrøm-Lang assumption. The latter is usually used for macromolecules.

Domain, Boundary, and Pair Nodes for the Electrophoretic Transport

Interface
The interface has the following domain, boundary, and pair nodes, listed in
alphabetical order, available from the Physics ribbon toolbar (Windows users), Physics
context menu (Mac or Linux users), or by right-clicking to access the context menu
(all users).

To add a node, go to the Physics toolbar, no matter what operating system

you are using. Subnodes are available by clicking the parent node and
selecting it from the Attributes menu.

• Ampholyte • No Flux
• Concentration • Outflow
• Current • Porous Matrix Properties
• Current Density • Potential
• Current Source • Protein
• Flux • Species Source
• Fully Dissociated Species • Solvent
• Inflow • Uncharged Species
• Initial Concentration • Weak Acid
• Initial Potential • Weak Base
• Insulation

206 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

 For axisymmetric components, COMSOL Multiphysics takes the axial
symmetry boundaries (at r = 0) into account and automatically adds an
Axial Symmetry node that is valid on boundaries representing the
symmetry axis.

In the COMSOL Multiphysics Reference Manual, see Table 2-3 for links
to common sections and Table 2-4 for common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Solvent
The settings of this node are used to define the properties of the aqueous solvent.

If Convection is enabled on the interface top node, you can specify the Velocity field
(m/s) as user defined input using analytical expressions or the velocity field variables
solved for by a separate physics interface.

The Solvent node automatically defines the concentration variables and for protons
(<name>.cH) and hydroxide ions (<name>.cOH), and the corresponding flux
expressions. See Diffusion and Migration Settings for how to set up the transport
parameters for the proton and hydroxide ions.

In the Solvent Properties section you can modify the Dynamic viscosity (Pa·s) and
Relative permittivity (unitless) values. The Built in and default values are applicable to
water. These parameters are used when calculating mobilities according to the
Debye-Hückel-Henry relation in the species nodes.

In the Water Self-Ionization section you can change the default Built in expression for
the Water self-ionization constant, pKw (unitless), to any user defined expression.

Porous Matrix Properties

Use this node, available if Mass transfer in porous media has been enabled on the
interface top-node, to define the Porosity (electrolyte volume fraction) and Tortuosity
of a domain.

The porosity should be a number between 0 and 1.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 207

 Fully Dissociated Species
Use this node to define a fully dissociated charged species, such as strong bases and
acids.

The Charge number, Z0 (unitless), defines the species charge.

See also Common Settings for the Species nodes in the Electrophoretic Transport
Interface and Diffusion and Migration Settings.

Uncharged Species
Use this node to define a species that does not carry any charge, nor is impacted by the
electric field.

See also Common Settings for the Species nodes in the Electrophoretic Transport
Interface and Diffusion and Migration Settings.

Weak Acid
The Weak acid node supports multiple dissociation steps, where the acid of the first
dissociation step is uncharged.

The species may be either Monoprotic, subject to one dissociation step only, or
Polyprotic. For the latter case any Number of dissociation steps larger than one may be
used.

See also Common Settings for the Species nodes in the Electrophoretic Transport
Interface and Diffusion and Migration Settings.

Weak Base
The Weak base node supports multiple dissociation steps, where the base of the last
dissociation step is uncharged.

The species may be either Monoprotic, subject to one dissociation step only, or
Polyprotic. For the latter case any Number of dissociation steps larger than one may be
used.

Note that the pKa refers to the acid constant of the conjugate acid of the weak base.

See also Common Settings for the Species nodes in the Electrophoretic Transport
Interface and Diffusion and Migration Settings.

208 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Ampholyte
Use the Ampholyte node generically to define any species where the average charge
depends on the pH of the solution. The Dissociation model may be based either on a
set of Equilibrium constants or an Average charge.

When using the Equilibrium constants the Base charge in last dissociation step, Z0
(unitless), needs to be set.

The Average charge, Z (unitless) parameter is typically a function of pH and may be

added as an analytical function or an interpolation polynomial under Definitions. The
average squared charge, used in the electrolyte potential equation, is calculated
automatically based on Z .

See also Common Settings for the Species nodes in the Electrophoretic Transport
Interface and Diffusion and Migration Settings.

Protein
Use the Protein node to define macromolecules. The features of the Protein node are
similar to the Ampholyte node, but with the default settings applicable for larger
molecules.

See also Common Settings for the Species nodes in the Electrophoretic Transport
Interface and Diffusion and Migration Settings.

Current Source
To make this node available, click the Show button ( ) and select Advanced Physics
Options.

Use this node to add a current source in a domain. A current source may appear in a
domain in homogenized porous electrode modeling, but should normally not be used.

Initial Potential
Use this node to specify the Initial Value of the electrolyte potential for the solver.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 209

 Current
The Current boundary condition sets the total current or average current density over
a boundary. It will set a constant electrolyte potential along the given boundary, that
satisfies the current value setting.

This node is typically used to model electrode surfaces or boundaries facing an

electrolyte reservoir (containing an electrode).

When using the Total current option in 1D or 2D, the boundary area is based either
on the Cross sectional area (1D) or the Out-of-Plane thickness (2D) properties, set on
the physics interface top node.

Current Density
Use the Current Density node to specify the current density distribution along a
boundary.

This node is typically used to model electrode surfaces where the electrode kinetics
depends on the electrolyte potential.

Note that using this node in 2D or 3D may result in an uneven potential distribution
along the boundary. To mitigate such effects you may use the Current node instead.

Insulation
The Insulation boundary condition describes the walls of a cell or the boundaries of the
cell that do not face an electrode (or a reservoir containing an electrode). The
boundary condition imposes the following equation:

il ⋅ n = 0

Potential
Add the Potential node on a boundary to set a fixed potential. This node is typically
used to model electrode surfaces or boundaries facing an electrolyte reservoir.

The node sets the potential in the electrolyte, φ l, to be equal to the Boundary
electrolyte potential, φ l, bnd (SI unit: V).

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.

210 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Species Source
To make this node available, click the Show button ( ) and select Advanced Physics
Options.

This node may be added as a subnode to any species node. See also Common Settings
for the Species nodes in the Electrophoretic Transport Interface.

In order to account for consumption or production of species, for example in porous

electrodes or as a result of reversible reactions, the Species Source node adds source
terms expressions S (SI unit: mol/(m3·s) to the right-hand side of the transport
equation of the parent species.

Initial Concentration
This node may be added as a subnode to any species node. See also Common Settings
for the Species nodes in the Electrophoretic Transport Interface.

This node specifies the initial value for the Concentration, c (mol/m3), of the parent
species. This value serve as the initial condition for a transient simulation. The value
also serves as a start guess for stationary problems.

You can use spatially dependent functions (such as smoothed step functions) available
under Definitions when defining the Concentration expression to specify different
concentrations in different parts of the geometry. You can also use additional Initial
Values node and modify the Selection to set different values for different domains.

Concentration
This node may be added as a subnode to any species node. See also Common Settings
for the Species nodes in the Electrophoretic Transport Interface

This condition node adds a boundary condition for the parent species concentration.
Use the node to, for instance, specify the inlet concentration at the boundary facing a
electrolyte reservoir.

No Flux
This node may be added as a subnode to any species node. See also Common Settings
for the Species nodes in the Electrophoretic Transport Interface.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 211

 This node is the default boundary condition on exterior boundaries. It represents
boundaries where no mass flows in or out of the boundaries. Hence, the total flux is
zero.

Flux
This node may be added as a subnode to any species node. See also Common Settings
for the Species nodes in the Electrophoretic Transport Interface.

This node can be used to specify the species inward flux across a boundary. The flux
can represent a flux from or into a much larger surrounding environment, a phase
change, or a flux due to chemical reactions.

INWARD FLUX
Enter a value or expression for the species mass flux J0. Use a minus sign when
specifying a flux directed out of the system.

External convection
Set Flux type to External convection to prescribe a flux to or from an exterior domain
(not modeled) assumed to include convection. The exterior can for example include a
forced convection to control the temperature or to increase the mass transport. In this
case the prescribed mass flux corresponds to

J0 = kc ( cb – c )

where kc is a mass transfer coefficient and cb is the bulk concentration, the typical
concentration far into the surrounding exterior domain.

Inflow
This node is available when you select the Convection check box on the physics interface
Settings window.

Use this node to specify the species concentrations at an inlet boundary.

BOUNDARY CONDITION TYPE

The option Concentration constraint constrains the concentration values on the
boundary by the use of pointwise constraints. When using this option the boundary
condition is identical to the Concentration node.

The other option, Flux (Danckwerts) can be more stable and fast to solve when high
reaction rates are anticipated in the vicinity of the inlet. Oscillations on the solutions

212 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

can also be avoided in such cases. The latter condition uses a flux boundary condition
based on the velocity across the boundary and the concentration values.

Outflow
Set this condition at outlets where species are transported out of the model domain by
migration or fluid motion. It is assumed that migration and convection is the
dominating transport mechanism across outflow boundaries, and therefore that
diffusive transport can be ignored, that is:

n ⋅ ( – D ∇c ) = 0

THE ELECTROPHORETIC TRANSPORT INTERFACE | 213

 The Surface Reactions Interface
The Surface Reactions (sr) interface ( ), found under the Chemical Species Transport
branch ( ) when adding a physics interface, is used to model the chemical reactions
of surface and bulk species on a boundary. Surface species can be transported in the
tangential direction of the surface by Fick’s law whereas bulk species are assumed to be
immobile on the surface.

The physics interface supports simulation of surface reactions on boundaries in 1D,

2D, and 3D as well as for axisymmetric components in 1D and 2D. The dependent
variables are the surface concentrations, cs,i (SI unit: mol/m2) and the bulk
concentrations, cb,i (SI unit: mol/m2).

When this physics interface is added, these default nodes are also added to the Model
Builder—Surface Properties, No Flux, and Initial Values. Then, from the Physics toolbar,
add other nodes that implement, for example, boundary conditions. You can also
right-click Surface Reactions to select physics features from the context menu.

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is sr.

DEPENDENT VARIABLES
Add or remove species and also change the names of the dependent variables that
represent the species concentrations. Note that the names can be changed but the
names of fields and dependent variables must be unique within a model.

Enter the Number of surface species. Use the Add surface concentration ( ) and
Remove surface concentration ( ) buttons as needed. The same number of Surface
concentrations cs, cs2, cs3...are then listed in the table.

214 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Enter the Number of bulk species. Use the Add bulk concentration ( ) and Remove bulk
concentration ( ) buttons as needed. The same number of Bulk concentrations cb,
cb2, cb3...are then listed in the table.

DISCRETIZATION
To display all settings available in this section, click the Show button ( ) and select
Advanced Physics Options.

CONSISTENT AND INCONSISTENT STABILIZATION

To display these sections, click the Show button ( ) and select Stabilization.

By default the Compensate for boundary stretching check box is selected for the Surface
Properties node. This section is then used to stabilize the tangential mesh velocity
term.

When the Compensate for boundary stretching check box is cleared (not selected), and
for fixed geometries or moving geometries, the stabilization has no effect.

See Surface Reaction Equations on Deforming Geometries for more information.

• Boundary, Edge, Point, and Pair Nodes for the Surface Reactions
Interface
• Theory for the Surface Reactions Interface

Boundary, Edge, Point, and Pair Nodes for the Surface Reactions
Interface
The Surface Reactions InterfaceThe Surface Reactions Interface has these boundary,
edge, point, and pair nodes, listed in alphabetical order, available from the Physics
ribbon toolbar (Windows users), Physics context menu (Mac or Linux users), or
right-click to access the context menu (all users).

In general, to add a node, go to the Physics toolbar, no matter what

operating system you are using.Subnodes are available by clicking the
parent node and selecting it from the Attributes menu.

These nodes are described in this section:

• Initial Values

THE SURFACE REACTIONS INTERFACE | 215

 • Reactions
• Surface Concentration
• Surface Properties

All other available nodes are described for the Transport of Diluted Species interface.
See Domain, Boundary, and Pair Nodes for the Transport of Diluted Species Interface.

In the COMSOL Multiphysics Reference Manual see Table 2-3 for links
to common sections and Table 2-4 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Surface Properties
Use the Surface Properties node to define the density of sites, the site occupancy
number, and the surface diffusion.

SPECIES CONSERVATION ON DEFORMING GEOMETRY

The Compensate for boundary stretching check box is selected by default. Click to clear
the check box if required.

SITES
Enter a value or expression for the Density of sites Γs (SI unit: mol/m2). The default
is 2 x 10-5 mol/m2.

Enter a Site occupancy number σi (dimensionless), indicating how many surface sites a
surface species block upon adsorption.

This section is only present if the number of surface species is 1 or higher.

SURFACE DIFFUSION
Select a Surface material from the list. The default is None.

For each surface concentration species, the default Diffusion coefficient Di

(SI unit: m2/s) is User defined. Select Isotropic, Diagonal, Symmetric, or Anisotropic
depending on the characteristics of the surface, and then enter values or expressions in
the field or matrix.

This section is only present if the number of surface species is 1 or higher.

216 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

BULK SPECIES
For each bulk species enter the Molar mass Mi (SI unit: kg/mol) and the Density ρi
(SI unit: kg/m3). The default molar mass is 0.144 kg/mol and the default density is
5320 kg/m3).

This section is only present if the number of bulk species is 1 or higher.

Surface Reaction Equations on Deforming Geometries

Initial Values
The Initial Values node allows the initial value or guess for the surface and bulk
concentrations.

INITIAL VALUES
Based on the number of surface species and number of bulk species entered for the
physics interface under Dependent Variables section, enter values for the same number
of Surface concentration cs, cs2, cs3,... (SI unit: mol/m2) and Bulk concentration cb,
cb2, cb3,... (SI unit: mol/m2) in each field.

Reactions
The Reactions node adds rate expression terms to the species transport equations in
order to account for consumption or production of species due to reactions.

REACTION RATE FOR SURFACE SPECIES

Add a reaction rate expression, Rs,cs1,cs2...(SI unit: mol/(m2·s)), for each surface
species taking part in a surface reaction.

This section is only present if the number of surface species is 1 or higher.

REACTION RATE FOR BULK SPECIES

Add a reaction rate expression, Rb,cb1,cb2...(SI unit: mol/(m2·s)), for each bulk species
taking part in a surface reaction.

This section is only present if the number of bulk species is 1 or higher.

THE SURFACE REACTIONS INTERFACE | 217

 Surface Concentration
Use the Surface Concentration node to set the surface concentrations for one or more
species on an edge (3D components) or a point (2D and 2D axisymmetric
components).

SURFACE CONCENTRATION
Select each species check box as needed and enter a value or expression for each species
concentration, cs,0,cs1,cs2... (SI unit: mol/(m2·s)).

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.

218 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

T he o r y f o r t he Tran sp ort of D i l u t ed
S pe c i e s Inte r f a c e
The Transport of Diluted Species Interface provides a predefined modeling
environment for studying the evolution of chemical species transported by diffusion
and convection as well as migration due to an electric field. The physics interface
assumes that all species present are dilute; that is, that their concentration is small
compared to a solvent fluid or solid. As a rule of thumb, a mixture containing several
species can be considered dilute when the concentration of the solvent is more than
90 mol%. Due to the dilution, mixture properties such as density and viscosity can be
assumed to correspond to those of the solvent.

When studying mixtures that are not dilute, the mixture and transport properties
depend of the composition, and a different physics interface is recommended. See The
Transport of Concentrated Species Interface for more information.

Fick’s law governs the diffusion of the solutes, dilute mixtures or solutions, while the
phenomenon of ionic migration is sometimes referred to as electrokinetic flow. The
Transport of Diluted Species interface supports the simulations of chemical species
transport by convection, migration, and diffusion in 1D, 2D, and 3D as well as for
axisymmetric components in 1D and 2D.

In this section:

• Mass Balance Equation • Adding Transport Through

• Equilibrium Reaction Theory Migration

• Convective Term Formulation • Theory for the Reactive Pellet Bed

• Solving a Diffusion Equation Only • Supporting Electrolytes

• Mass Sources for Species Transport • Danckwerts Inflow Boundary

Condition
• Crosswind Diffusion
• References

The Transport of Diluted Species in Porous Media Interface theory is also included.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 219

 Mass Balance Equation
The default node attributed to the Transport of Diluted Species interface models
chemical species transport through diffusion and convection and solves the mass
conservation equation for one or more chemical species i:

∂c i
------- + ∇ ⋅ ( – D ∇c i ) + u ⋅ ∇c i = R i (4-6)
∂t

Equation 4-6 in its form above includes the transport mechanisms diffusion and
convection. If Migration in Electric Field is activated (only available in some add-on
products), the migration mechanism will be added to the equation as well. See more
details in the section Adding Transport Through Migration.

• ci is the concentration of the species (SI unit: mol/m3)

• Di denotes the diffusion coefficient (SI unit: m2/s)
• Ri is a reaction rate expression for the species (SI unit: mol/(m3·s))
• u is the velocity vector (SI unit: m/s)
The flux vector N (SI unit: mol/(m2·s)) is associated with the mass balance equation
above and used in boundary conditions and flux computations. For the case where the
diffusion and convection are the only transport mechanisms, the flux vector is defined
as

N i = – D ∇c + u c (4-7)

If Migration in Electric Fields is activated, the flux vector is amended with the
migration term as show in the section Adding Transport Through Migration.

The first term on the left-hand side of Equation 4-6 corresponds to the accumulation
(or indeed consumption) of the species.

The second term accounts for the diffusive transport, accounting for the interaction
between the dilute species and the solvent. A user input field for the diffusion
coefficient is available. Anisotropic diffusion coefficient tensor input is supported.

The third term on the left hand side of Equation 4-6 describes the convective transport
due to a velocity field u. This field can be expressed analytically or be obtained from
coupling this physics interface to one that computes fluid flow, such as Laminar Flow.

On the right-hand side of the mass balance equation (Equation 4-6), Ri represents a
source or sink term, typically due to a chemical reaction, or /desorption on a porous
matrix. To specify Ri, another node must be added to the Transport of Diluted Species

220 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

interface—the Reaction node, which has a field for specifying a reaction equation using
the variable names of all participating species.

Equilibrium Reaction Theory

The feature Equilibrium Reaction is described in this section. A chemical equilibrium
reaction system is defined by the stoichiometry of the reaction and the relation
between the chemical activities of the chemical species participating in the reaction (the
equilibrium condition).

The kinetics of the reaction is so fast that the equilibrium condition is fulfilled at all
times in all space coordinates.

The equilibrium condition is commonly based on the stoichiometric coefficients,

νi (dimensionless), of the reaction, the species activities of the reacting species
ai (dimensionless), and an equilibrium constant, Keq (1) according to:

ν
∏ ai i
i ∈ products
K eq = ----------------------------------
–ν
∏ ai i
i ∈ reactants

where the species activities are defined as

ci
a i = γ c, i -------
c a0

where ca0 (SI unit: mol/m3) is the standard molarity, and γc,i (dimensionless) an
activity coefficient.

Defining the stoichiometric coefficients positive for products and negative for
reactants, the above equilibrium condition can also be written:

νi
K eq = ∏ ai
i

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 221

 The Equilibrium Reaction node solves for a reaction rate so that the equilibrium
condition is always fulfilled in the domain.

γc,i is set to unity when the Equilibrium constant is selected on the

Settings window. For non-unity activity coefficients, a user defined
equilibrium condition can be used.

EQUILIBRIUM REACTIONS AND INFLOW BOUNDARY CONDITIONS

Contradictory constraints arise if the boundary conditions for concentrations or
activities are set so that the domain equilibrium condition is not fulfilled. Special
treatment is therefore needed at Inflow boundaries, where the concentrations are set
for all species in the mass transport interfaces.

One way of avoiding competing constraints on an inflow boundary is to add an

additional reaction coordinate degree of freedom, solved for to create a set of modified
inflow concentrations that fulfill the domain equilibrium condition. The reaction
coordinate gives rise to a concentration shift, which is the offset to the inflow
concentrations provided by the user. The shift for each species obeys the stoichiometry
of the reaction and the equilibrium expression. The modified inflow concentrations are
then used in the boundary conditions for the domain mass transport equations. The
resulting modified inflow concentrations can be seen as the stationary solution for a
batch reactor with the user inflow concentrations as initial concentrations. In addition,
the domain reaction rate degree of freedom of the equilibrium reaction is constrained
to zero on all Inflow boundaries.

EQUILIBRIUM REACTIONS AND CONCENTRATION BOUNDARY

CONDITIONS
No special treatment is made with regards to input concentration values of the
Concentration boundary node. Using this feature, you can explicitly set one or a set of
concentrations, and the equilibrium condition acts on the rest of the concentrations.
However, there is no solution to the problem if more concentrations than the number
of species minus the number of equilibrium reactions are set using this feature.

EQUILIBRIUM REACTIONS AND TIME-DEPENDENT SIMULATIONS

Spurious oscillations may occur in a time-dependent problem if the initial conditions
do not fulfill the equilibrium condition. Since equilibrium reactions are assumed to be
infinitely fast, the solution is to initialize the problem using an additional study step,

222 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

solving for a stationary problem with all non-equilibrium reaction rates set to zero.
Manual scaling of the reaction rate dependent variables is needed in this study step.

Convective Term Formulation

The default node attributed to The Transport of Diluted Species Interface assumes
chemical species transport through diffusion and convection (a check box to activate
migration is available) and implements the mass balance equation in Equation 4-6.

There are two ways to present a mass balance where chemical species transport occurs
through diffusion and convection. These are the non-conservative and conservative
formulations of the convective term:

∂c
non-conservative: ----- + u ⋅ ∇c = ∇ ⋅ ( D ∇c ) + R (4-8)
∂t

∂c
conservative: ----- + ∇ ⋅ ( cu ) = ∇ ⋅ ( D ∇c ) + R (4-9)
∂t

and each is treated slightly differently by the solver algorithms. In these equations D
(SI unit: m2/s) is the diffusion coefficient, R (SI unit: mol/(m3·s)) is a production or
consumption rate expression, and u (SI unit: m/s) is the solvent velocity field. The
diffusion process can be anisotropic, in which case D is a tensor.

If the conservative formulation is expanded using the chain rule, then one of the terms
from the convection part, c∇·u, would equal zero for an incompressible fluid and
would result in the non-conservative formulation above. This is in fact the default
formulation in this physics interface and ensures that nonphysical source terms do not
emerge from a solution for the flow field. To switch between the two formulations,
click the Show button ( ) and select Advanced Physics Options.

Solving a Diffusion Equation Only

Remove the convection term from Equation 4-8 and Equation 4-9 by clearing the
Convection check box in the Transport Mechanisms section for The Transport of
Diluted Species Interface. The equation then becomes

∂----c-
= ∇ ⋅ ( D ∇c ) + R
∂t

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 223

 Mass Sources for Species Transport
There are two types of mass sources in the Transport of Diluted Species interface: point
sources and line sources.

Note: The features below are only available in a limited set of add-on products. For a
detailed overview of which features are available in each product, visit
http://www.comsol.com/products/specifications/

POINT SOURCE
·
A point source is theoretically formed by assuming a mass injection/ejection, Q c (SI
3
unit: mol/(m ·s)), in a small volume δV and then letting the size of the volume tend
to zero while keeping the total mass flux constant. Given a point source strength, q· p,c
(SI unit: mol/s), this can be expressed as

·
lim  Qc = q· p,c (4-10)
δV → 0
δV

An alternative way to form a point source is to assume that mass is injected/extracted

through the surface of a small object. Letting the object surface area tend to zero while
keeping the mass flux constant, results in the same point source. For this alternative
approach, effects resulting from the physical object’s volume need to be neglected.

The weak contribution

q· p,c test ( c )
·
is added at a point in the geometry. As can be seen from Equation 4-10, Q c must tend
to plus or minus infinity as δV tends to zero. This means that in theory the
concentration also tends to plus or minus infinity.

Observe that “point” refers to the physical representation of the source. A point source
can therefore only be added to points in 3D components and to points on the
symmetry axis in 2D axisymmetry components. Other geometrical points in 2D
components represent physical lines.

The finite element representation of Equation 4-10 corresponds to a finite

concentration at a point with the effect of the point source spread out over a region
around the point. The size of the region depends on the mesh and on the strength of

224 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

the source. A finer mesh gives a smaller affected region, but also a more extreme
concentration value. It is important not to mesh too finely around a point source since
this can result in unphysical concentration values. It can also have a negative effect on
the condition number for the equation system.

LINE SOURCE
·
A line source can theoretically be formed by assuming a source of strength Q l,c (SI
3
unit: mol/(m ·s)), located within a tube with cross-section δS and then letting δS
tend to zero while keeping the total mass flux per unit length constant. Given a line
source strength, q· l,c (SI unit: mol/(m·s)), this can be expressed as

·
lim  Ql,c = q· l,c (4-11)
δS → 0
δS

As in the point source case, an alternative approach is to assume that mass is injected/
extracted through the surface of a small object. This results in the same mass source,
but requires that effects resulting from the physical object’s volume are neglected.

The weak contribution

q· l,c test ( c )

is added on lines in 3D or at points in 2D (which represent cut-through views of lines).

Line sources can also be added on the axisymmetry line in 2D axisymmetry
components. It cannot, however, be added on geometrical lines in 2D since those
represent physical planes.

As with a point source, it is important not to mesh too finely around the line source.

For feature node information, see Line Mass Source and Point Mass
Source in the COMSOL Multiphysics Reference Manual.

Adding Transport Through Migration

Note: Migration is only available in a limited set of add-on products. For a detailed
overview of which features are available in each product, visit
http://www.comsol.com/products/specifications/

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 225

 In addition to transport due to convection and diffusion, the Transport of Diluted
Species interface supports ionic species transport by migration. This is done by
selecting the Migration in Electric Field check box under the Transport Mechanisms
section for the physics interface. The mass balance then becomes:

∂c i
+ ∇ ⋅ ( – D i ∇c i – z i u m, i F c i ∇V + c i u ) = R i (4-12)
∂t

where

• ci (SI unit: mol/ m3) denotes the concentration of species i

• Di (SI unit: m2/s) is the diffusion coefficient of species i
• u (SI unit: m/s) is the fluid velocity
• F (SI unit: A·s/mol) refers to Faraday’s constant
• V (SI unit: V) denotes the electric potential
• zi (dimensionless) is the charge number of the ionic species, and
• um,i (SI unit: mol·s/kg) its ionic mobility

The velocity, u, can be a computed fluid velocity field from a Fluid Flow interface or
a specified function of the spatial variables x, y, and z. The potential can be provided
by an expression or by coupling the system of equations to a current balance, such as
the ElectrostaticsSecondary Current Distribution interface. Sometimes it is assumed to
be a supporting electrolyte, which simplifies the transport equations.

The Nernst-Einstein relation can in many cases be used for relating the species mobility
to the species diffusivity according to

Di
u m, i = --------
RT

where R (SI unit: J/(mol·K)) is the molar gas constant and T (SI unit: K) the
temperature.

226 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Note: With regards to migration, the assumption in the Transport of Diluted Species
Interface is that the concentrations are so low that each ionic species does not
contribute to a net charge in the solution. If this assumption does not hold, the
physics interface called Nernst-Planck Equations needs to be used. This latter
includes an electroneutrality condition and also computes the electric potential field
in the electrolyte. For more information, see Theory for the Nernst-Planck Equations
Interface. This interface is included in the Chemical Reaction Engineering Module.

Supporting Electrolytes
In electrolyte solutions, a salt can be added to provide a high electrolyte conductivity
and decrease the ohmic losses in a cell. These solutions are often called supporting
electrolytes, buffer solutions, or carrier electrolytes. The added species, a negative and
a positive ion pair predominates over all other species. Therefore, the supporting
electrolyte species can be assumed to dominate the current transport in the solution.
In addition, the predominant supporting ions are usually selected so that they do not
react at the electrode surfaces since the high conductivity should be kept through the
process, that is, they should not be electro-active species. This also means that the
concentration gradients of the predominant species in a supporting electrolyte are
usually negligible.

Modeling and solving for a supporting electrolyte in the Electrostatics or Secondary

Current Distribution interfaces will give a potential distribution that drives the
migration in the Transport of Diluted Species Interface.

The current density vector is proportional to the sum of all species fluxes as expressed
by Faraday’s law:

i = F  zi Ni
i

The electroneutrality condition ensures that there is always a zero net charge at any
position in a dilute solution. Intuitively, this means that it is impossible to create a
current by manually pumping positive ions in one direction and negative ions in the
other. Therefore, the convective term is canceled out to yield the following expression
for the electrolyte current density, where j denotes the supporting species:

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 227

  –zj um, j F cj ∇φ
2
i = F (4-13)
j

Equation 4-13 is simply Ohm’s law for ionic current transport and can be simplified to

i = – κ ∇φ (4-14)

where κ is the conductivity of the supporting electrolyte. A current balance gives the
current and potential density in the cell

∇⋅i = 0

which in combination with Equation 4-14 yields:

∇ ⋅ ( – κ ∇φ ) = 0 (4-15)

Equation 4-15 can be easily solved using the Electrostatics or Secondary Current
Distribution interface and, when coupled to the Transport in Diluted Species interface,
the potential distribution shows up in the migration term.

Crosswind Diffusion
Transport of diluted species applications can often result in models with very high cell
Péclèt number—that is, systems where convection or migration dominates over
diffusion. Streamline diffusion and crosswind diffusion are of paramount importance
to obtain physically reasonable results. The Transport of Diluted Species interface
provides two crosswind diffusion options using different formulations. Observe that
crosswind diffusion makes the equation system nonlinear even if the transport
equation is linear.

DO CARMO AND GALEÃO

This is the formulation described in Numerical Stabilization. The method reduces
over- and undershoots to a minimum, even for anisotropic meshes.

In some cases, the resulting nonlinear equation system can be difficult to converge.
This can happen when the cell Péclèt number is very high and the model contains
many thin layers such as contact discontinuities. You then have three options:

• Refine the mesh, especially in regions with thin layers.

• Use a nonlinear solver with a constant damping factor less than one.
• Switch to the Codina crosswind formulation.

228 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

CODINA
The Codina formulation is described in Ref. 1. It adds diffusion strictly in the direction
orthogonal to the streamline direction. Compared to the do Carmo and Galeão
formulation, the Codina formulation adds less diffusion but is not as efficient at
reducing over- and undershoots. It also does not work as well for anisotropic meshes.
The advantage is that the resulting nonlinear system is easier to converge and that
under-resolved gradients are less smeared out.

Danckwerts Inflow Boundary Condition

Constraining the composition to fixed values at an inlet to a reactor may sometimes
result in issues with unreasonably high reaction rates or singularities at the inlet
boundary. These problems may many times be mitigated by using a flux boundary
condition instead, based on the inlet concentrations and the fluid velocity. In chemical
engineering this type of flux boundary condition is also known as a Danckwerts
condition.

Use the Danckwerts condition to specify inlet concentrations to domains where high
reaction rates are anticipated in the vicinity to the inlet (Ref. 2).

Given an inlet concentration ci,0 the Danckwerts inflow boundary condition reads

n⋅Ni = n ⋅ (u ci,0)

See further:

Inflow

Transport of Diluted Species in Porous Media

VARIABLY SATURATED POROUS MEDIA

The following equations for the concentrations, ci, describe the transport of solutes in
a variably saturated porous medium for the most general case, when the pore space is
primarily filled with liquid but also contain pockets or immobile gas:

∂ ∂ ∂
( θc i ) + ( ρ b c P, i ) + (a v c G, i) + u ⋅ ∇c i =
∂t ∂t ∂t (4-16)
∇ ⋅ [ ( D D, i + D e, i ) ∇c i ] + R i + S i

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 229

 On the left-hand side of Equation 4-16, the first three terms correspond to the
accumulation of species within the liquid, solid, and gas phases, while the last term
describes the convection due to the velocity field u (SI unit: m/s).

In Equation 4-16 ci denotes the concentration of species i in the liquid (SI unit: mol/
m3), cP, i the amount adsorbed to (or desorbed from) solid particles (moles per unit
dry weight of the solid), and cG, i the concentration of species i in the gas phase.

The equation balances the mass transport throughout the porous medium using the
porosity εp, the liquid volume fraction θ; the bulk (or drained) density, ρb = (1 − εp)ρ,
and the solid phase density ρ (SI unit: kg/m3).

For saturated porous media, the liquid volume fraction θ is equal to the porosity εp,
but for partially saturated porous media, they are related by the saturation s as θ = sεp.
The resulting gas volume fraction is av = εp − θ = (1-s)εp.

On the right-hand side of Equation 4-16, the first term introduces the spreading of
species due to mechanical mixing () as well as from diffusion and volatilization to the
gas phase. The tensor is denoted DD (SI unit: m2/s) and the effective diffusion by De
(SI unit: m2/s).

The last two terms on the right-hand side of Equation 4-16 describe production or
consumption of the species; Ri is a reaction rate expression which can account for
reactions in the liquid, solid, or gas phase, and Si is an arbitrary source term, for
example due to a fluid flow source or sink.

In order to solve for the solute concentration of species i, ci, the solute mass sorbed to
solids cP,i and dissolved in the gas-phase cG,i are assumed to be functions of ci.
Expanding the time-dependent terms gives

∂ θc ∂
( i ) + ∂ ( ρ b c P, i ) + (a v c G, i) =
∂t ∂t ∂t
(4-17)
∂c i ∂θ ∂ε p
( θ + ρ b k P, i + a v k G, i ) + ( 1 – k G, i )c i – ( ρ P c P, i – k G, i c i )
∂t ∂t ∂t

where kP,i = ∂cP,i/∂ci is the adsorption isotherm and kG,i = ∂cG,i/∂ci is the linear
volatilization. Equation 4-16 can then be written as

∂c i ∂θ ∂ε p
( θ + ρ b k P, i + a v k G, i ) + ( 1 – k G, i )c i – ( ρ P c P, i – k G, i c i ) + u ⋅ ∇c i
∂t ∂t ∂t (4-18)
= ∇ ⋅ [ ( D D + D e ) ∇c i ] + R i + S i

230 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

SATURATED POROUS MEDIA
In the case of transport in a saturated porous medium, θ = εp and the governing
equations are

∂c i ∂ε p
( ε p + ρ b k P, i ) + ( c i – ρ P c P, i ) + u ⋅ ∇c i =
∂t ∂t (4-19)
∇ ⋅ [ ( D D, i + θτ F, i D F, i ) ∇c i ] + R i + S
i

Convection
Convection describes the movement of a species, such as a pollutant, with the bulk
fluid velocity. The velocity field u corresponds to a superficial volume average over a
unit volume of the porous medium, including both pores and matrix. This velocity is
sometimes called Darcy velocity, and defined as volume flow rates per unit cross
section of the medium. This definition makes the velocity field continuous across the
boundaries between porous regions and regions with free flow.

The velocity field to be used in the Model Inputs section on the physics
interface can, for example, be prescribed using the velocity field from a
Darcy’s Law or a Brinkman Equations interface.

The average linear fluid velocities ua, provides an estimate of the fluid velocity within
the pores:

u
u a = ----- Saturated
εp
u
u a = ---- Partially saturated
θ

where εp is the porosity and θ = sεp the liquid volume fraction, and s the saturation, a
dimensionless number between 0 and 1.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 231

 Figure 4-1: A block of a porous medium consisting of solids and the pore space between the
solid grains. The average linear velocity describes how fast the fluid moves within the pores.
The Darcy velocity attributes this flow over the entire fluid-solid face.

Convective Term Formulation

The Transport of Diluted Species in Porous Media interface includes two formulations
of the convective term. The conservative formulation of the species equations in
Equation 4-16 is written as:

∂ θc ∂
( i ) + ∂ ( ρ b c P, i ) + (a v c G, i) + ∇ ⋅ uc i =
∂t ∂t ∂t (4-20)
∇ ⋅ [ ( D D, i + D e, i ) ∇c i ] + R i + S i

If the conservative formulation is expanded using the chain rule, then one of the terms
from the convection part, ci∇·u, would equal zero for an incompressible fluid and
would result in the non-conservative formulation described in Equation 4-16.

When using the non-conservative formulation, which is the default, the fluid is
assumed incompressible and divergence free: ∇ ⋅ u = 0. The non-conservative
formulation improves the stability of systems coupled to a momentum equation (fluid
flow equation).

To switch between the two formulations, click the Show button ( ) and
select Advanced Physics Options. In the section Advanced Settings select
either Non-conservative form (the default) or Conservative form. The
conservative formulation should be used for compressible flow.

232 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Diffusion
The effective diffusion in porous media, De, depends on the structure of the porous
material and the phases involved. Depending on the transport of diluted species occurs
in free flow, saturated or partially saturated porous media, the effective diffusivity is
defined as:

De = DL Free Flow
εp
D e = ----- D L Saturated Porous Media
τL
θ
D e = ----- D L Partially Saturated Porous Media
τL
θ av
D e = ----- D L + ------ k G D G Partially Saturated with Volatilization
τL τG

Here DL and DG are the single-phase diffusion coefficients for the species diluted in
pure liquid and gas phases respectively (SI unit: m2/s), and τL and τG are the
corresponding tortuosity factors (dimensionless).

The tortuosity factor accounts for the reduced diffusivity due to the fact that the solid
grains impede Brownian motion. The interface provides predefined expressions to
compute the tortuosity factors in partially saturated porous media according to the
Millington and Quirk model (Ref. 12):

–7 ⁄ 3 2 –7 ⁄ 3 2
τF = θ ε , τG = av ε

and Bruggeman model

–5 ⁄ 2 2 –5 ⁄ 2 2
τF = θ ε , τG = av ε

For saturated porous media θ = εp. The fluid tortuosity for the Millington and Quirk
model is

–1 ⁄ 3
τF = εp

and for the Bruggeman model the tortuosity is defined as

–1 ⁄ 2
τF = εp

User defined expressions for the tortuosity factor can also be applied.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 233

 Dispersion
The contribution of dispersion to the mixing of species typically overshadows the
contribution from molecular diffusion, except when the fluid velocity is very small.

The spreading of mass, as species travel through a porous medium is caused by several
contributing effects. Local variations in fluid velocity lead to mechanical mixing
referred to as dispersion occurs because the fluid in the pore space flows around solid
particles, so the velocity field varies within pore channels. The spreading in the
direction parallel to the flow, or longitudinal dispersivity, typically exceeds the
transverse dispersivity from up to an order of magnitude. Being driven by the
concentration gradient alone, molecular diffusion is small relative to the mechanical
dispersion, except at very low fluid velocities.

Figure 4-2: Spreading of fluid around solid particles in a porous medium.

is controlled through the dispersion tensor DD. The tensor components can either be
given by user-defined values or expressions, or derived from the directional
dispersivities.

Using the longitudinal and transverse dispersivities in 2D, the dispersivity tensor
components are (Ref. 9):

2 2
ui uj
D Dii = α L ------- + α T -------
u u

ui uj
D Dij = D Dji = ( α L – α T ) -----------
u

In these equations, DDii (SI unit: m2/s) are the principal components of the
dispersivity tensor, and DDji and DDji are the cross terms. The parameters αL and αT
(SI unit: m) specify the longitudinal and transverse dispersivities; and ui (SI unit: m/
s) stands for the velocity field components.

234 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

In order to facilitate modeling of stratified porous media in 3D, the tensor formulation
by Burnett and Frind (Ref. 10) can be used. Consider a transverse isotropic media,
where the strata are piled up in the z direction, the dispersivity tensor components are:

2 2 2
u v w
D Lxx = α 1 ------- + α 2 ------- + α 3 -------
u u u
2 2 2
v u w
D Lyy = α 1 ------- + α 2 ------- + α 3 -------
u u u
2 2 2
w u v
D Lzz = α 1 ------- + α 3 ------- + α 3 -------
u u u (4-21)
uv
D Lxy = D Lyx = ( α 1 – α 2 ) -------
u
uw
D Lxz = D Lzx = ( α 1 – α 3 ) --------
u
vw
D Lyz = D Lzy = ( α 1 – α 3 ) --------
u

In Equation 4-21 the fluid velocities u, v, and w correspond to the components of the
velocity field u in the x, y, and z directions, respectively, and α1 (SI unit: m) is the
longitudinal dispersivity. If z is the vertical axis, α2 and α3 are the dispersivities in the
transverse horizontal and transverse vertical directions, respectively (SI unit: m).
Setting α2 = α3 gives the expressions for isotropic media shown in Bear (Ref. 9 and
Ref. 11).

Adsorption
As species travel through a porous medium they typically attach to (adsorb), and
detach (desorb) from the solid phase, which slows chemical transport through the
porous medium. Adsorption and desorption respectively reduces or increases species
concentrations in the fluid. The adsorption properties vary between chemicals, so a
plume containing multiple species can separate into components (Ref. 6). The physics
interface predefines three relationships to predict the solid concentrations, cPi from the
concentration in the liquid phase, ci:

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 235

 ∂c P ∂
cP = KP c -------- = ( K P c ) User defined
∂c ∂c
N ∂c P N–1
cP = KF c -------- = NK F c Freundlich (Ref. 3) (4-22)
∂c
K L c Pmax c ∂c P K L c Pmax
c P = ------------------------- -------- = ---------------------------
- Langmuir (Ref. 4, Ref. 5)
1 + KL c ∂c ( 1 + KL c )
2

The above equations contains the following parameters:

• User defined isotherm KP (dimensionless)

• Freundlich exponent N (dimensionless), Freundlich constant KF
(SI unit m3N·mol(1-N)/kg).
• Langmuir: maximum cPmax (SI unit mol/m3), Langmuir constant KL
(SI unit m3/mol).

These predefined expressions are adsorption isotherms that describe the amount of
species sorbed to the solid. Defined at equilibrium, the switch between liquid and solid
phases is instantaneous. In COMSOL Multiphysics, arbitrary expressions can be
entered to define, for example, non-equilibrium and temperature-dependent
adsorption laws, including those set out by Fetter (Ref. 7) and Bear and Verruijt
(Ref. 8).

The retardation factor, RF, describes how adsorption slows the solute velocity, uc,
relative to the average linear velocity of the fluid, ua, as in

ρ b ∂c P ua
RF = 1 + ------ -------- = ------
θ ∂c uc

If the contaminant moves at the average linear velocity of the fluid for RF = 1. For
RF > 1, the contaminant velocity is smaller than the fluid velocity owing to residence
time on solids.

Reactions
Chemical reactions of all types influence species transport in porous media. Examples
include biodegradation, radioactive decay, transformation to tracked products,
temperature- and pressure-dependent functions, exothermic reactions, and
endothermic reactions. The reactions represent change in species concentration per
unit volume porous medium per time. Reaction terms are used on the right-hand side

236 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

of the governing equation to represent these processes. For reactions in a fluid phase,
multiply the expression by the fluid volume fraction θ. Similarly, solid phase reaction
expressions include the bulk density, ρb, and gas phase reactions include the gas
volume fraction, av.

Theory for the Reactive Pellet Bed

The feature Reactive Pellet Bed, available to users of the Chemical Reaction
Engineering Module, adds to the transport of diluted species interface a domain
feature that can simulate regions filled with spherical reactive catalyst pellets, as in
packed bed reactors. The pellets are simulated with the Extra Dimension technology
provided by COMSOL: A 1D, 2D, or 3D domain comprises the bed volume. The
extra dimension is the added radial microscale dimension inside each pellet.

Outflow

Macroscale: c
Concentration in
fluid passing through
bed

Microscale:
cpe Concentration
in porous pellet
Inflow

Pellet of radius rpe

Figure 4-3: Schematic showing the macroscale (bed volume) and the microscale (pellet).

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 237

 The transport and reaction equations inside the pellets is done with an extra dimension
feature attached to the 1D, 2D, or 3D physics interfaces, including axisymmetric cases.

The equations inside the spherical pellet are solved as a spherical transport equations
on a non-dimensional radial coordinate on the domain 0-1. Different pellet radii and
even uneven radius distributions can be used.

The model equations assume spherical particles of a radius rpe. Consider the microscale
concentration cpe inside an individual porous pellet or particle, and the
macro-concentration c in the packed bed gas volume.

The pellet radius input can be:

• One uniform pellet radius, that can be space dependent f (x, y, z).
• Binary, ternary, and so on, mix up to 5 radii. The user inputs a table with the mix of
sizes (1 mm, 2 mm, for example), and a percentage of each. Different chemical
reactions per pellet size can be specified.

The model equation for the bulk (macroscale) species is, for example:

∂
ε b (c i) + u ⋅ ∇c i + ∇ ⋅ ( – D b, i ∇c i ) = R i (4-23)
∂t

• The dependent variable c for each chemical species i represents the interstitial
concentration (SI unit: mol/m3), that is, the physical concentration based on unit
volume of fluid flowing between the pellets.
• εb is the bed porosity (SI unit: 1). It should be noted that the R term on the right
hand side is per unit volume of bed, (SI unit: mol/(m3· s)).

Looking inside a pellet: Assuming no concentration variations in the space-angle (θ, ϕ)

direction, but only in the radial (r) direction of the spherical particle allows a
spherically symmetric reaction-diffusion transport equation inside the pellet. If rdim
(SI unit: m) is the spatial radial coordinate in the pellet, and rpe is the pellet radius, the
non-dimensional coordinate r=rdim/rpe can defined. The modeling domain on r goes
from 0 to 1.

238 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

 0 (center) r_pe (pellet perimeter)

0 1

Figure 4-4: Modeling domain in a pellet for a dimensional coordinate (top) and
non-dimensional coordinate (bottom).

A shell mole balance across a spherical shell at radius rdim (SI unit: m), and a
subsequent variable substitution r = rdim/rpe gives the following governing equation
inside the pellet on the domain 0<r<1:

 2 2 ∂ 2 2 2 
4πN  r r pe ε pe (c pe, i) + ∇ ⋅ ( – r D pe, i ∇c pe, i ) = r r pe R pe, i  (4-24)
 ∂ t 

where

• N is the number of pellets per unit volume of bed.

• Equally as in Equation 4-23, cpe is the interstitial (physical) species concentration in
moles/m3 fluid volume element inside the pore channel,
• Rpe is the reaction rate in moles/(m3· s) of particle volume. It should be stressed
that the user input of R is per unit volume of pellet.
The effective diffusion coefficient in Equation 4-23 and Equation 4-24 depends on
the porosity εpe, tortuosity τ, and physical gas diffusivity D in the porous particle
generally as

ε pe D
D pe = ------------ .
τ

The available tortuosity models for porous media are the Millington and Quirk
(Ref. 12),

–1 ⁄ 3 4⁄3
τ = ε pe  D pe = ε pe D, (4-25)

Bruggeman,

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 239

 –1 ⁄ 2 3⁄2
τ = ε pe  D pe = ε pe D (4-26)

and Tortuosity model, where the tortuosity expression is entered as user input:

ε pe D
D pe = ------------ (4-27)
τ

These are readily used for both gaseous and liquid fluids along with various types of
particle shapes. For instance, the first model has been shown to fit mass transport in
soil-vapor and soil-moisture wells.

Equation 4-23 can be solved for two types of boundary conditions at the interface
between the pellet surface and the fluid in this feature.

• Continuous concentrations: assuming that all resistance to mass transfer is within the
pellet and no resistance to pellet-fluid mass transfer on bulk fluid side. The
concentration in the fluid will thus be equal to that in the pellet pore just at the
pellet surface: c pe,i = c i . This constraint also automatically ensures flux continuity
between the pellet system and the free fluid system though so-called reaction forces
in the finite element formulation.
• Film resistance (mass flux): The flux of mass across the pellet-fluid interface into the
pellet is possibly rate determined on the bulk fluid side. The resistance is expressed
in terms of a film mass transfer coefficient, hDi, such that:
N i,inward = h D, i ( c ii – c pe, i ) , (4-28)

where Ni, inward is the molar flux from the free fluid into a pellet and has the SI unit
moles/(m2· s).

With the film resistance formulation, the free fluid Equation 4-23 needs to be
amended for flux continuity so that

∂
ε b (c i) + u ⋅ ∇c i + ∇ ⋅ ( – D b, i ∇c i ) = R i – N i,inward S b (4-29)
∂t

where Sb (SI unit: m2/m3) is the specific surface area exposed to the free fluid of the
packed bed (not including the inside of the pores).

For the case of randomly packed spherical particles, the specific surface area exposed
to the free fluid is (Ref. 3):

3
S b = ------- ( 1 – ε b ) (4-30)
r pe

240 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

The mass transfer coefficient in Equation 4-28 can be computed from the fluid
properties and flow characteristics within the porous media. For this, the Sherwood,
Sh, number defined as the ratio between the convective mass transfer coefficient and
the diffusive mass transfer coefficient is often used:

hL
Sh = --------
D

where L is a characteristic length (for spheres typically the radius) and D the diffusion
coefficient in the fluid. From the Sherwood number definition, the mass transfer
coefficient can be computed.

Three commonly used empirical expressions for the calculation of the Sherwood
number are the Frössling relation (Ref. 4):

1⁄2 1⁄3
Sh = 2 + 0.552Re Sc , (4-31)

which was measured on particles in the size region 1 mm, the Rosner relation (Ref. 5)

0.4 1⁄2 2⁄3

Sh = Sc ( 0.4Re + 0.2Re ), (4-32)

and the Garner and Keey relation (Ref. 4)

1⁄2 1⁄3
Sh = 0.94Re Sc , (4-33)

which was measured for Re numbers greater than 250.

All three depend on the Reynolds, Re, and Schmidt, Sc, numbers. The first describing
the fluid flow regime (laminar vs turbulent) and the second, the ratio between the
viscous diffusion rate and the molecular (mass) diffusion rate. In the expressions,
properties such as velocity, u, dynamic viscosity, μ, and density, ρ, of the fluid are
included.

ρuL
Re = -----------
μ

μ
Sc = --------
ρD

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 241

 References
1. R. Codina, “A discontinuity-capturing crosswind-dissipation for the finite element
solution of the convection-diffusion equation”, Computer Methods in Applied
Mechanics and Engineering, vol. 110, pp. 325–342, 1993.

2. P.V. Danckwerts, “Continuous flow systems: Distribution of residence times”,

Chem. Eng. Sci., vol. 2, no. 1, 1953.

3. J.M. Coulson and J.F. Richardson, Chemical Engineering, vol. 2, 4th ed.,
Pergamon Press, Oxford, U.K., 1991.

4. J.M. Coulson and J.F. Richardson, Chemical Engineering, vol. 1, 4th ed.,
Pergamon Press, Oxford, U.K., 1991.

5. D.E Rosner, Transport Processes in Chemically Reacting Flow Systems, ISBN-13:

978-1483130262, Butterworth-Heinemann, 1986

6. D.M. Mackay, D.L. Freyberg, P.V. Roberts, and J.A. Cherry, “A Natural Gradient
Experiment on Solute Transport in a Sand Aquifer: 1. Approach and Overview of
Plume Movement”, Water Resourc. Res., vol. 22, no. 13, pp. 2017–2030, 1986.

7. C.W. Fetter, Contaminant Hydrogeology, Prentice Hall, 1999.

8. J. Bear and A. Verruijt, Modeling Groundwater Flow and Pollution, D. Reidel

Publishing, 1994.

9. J. Bear, Hydraulics of Groundwater, McGraw-Hill, 1979.

10. R.D. Burnett and E.O. Frind, “An Alternating Direction Galerkin Technique for
Simulation of Groundwater Contaminant Transport in Three Dimensions: 2.
Dimensionality Effects”, Water Resour. Res., vol. 23, no. 4, pp. 695–705, 1987.

11. J. Bear, Dynamics of Fluids in Porous Media, Elsevier Scientific Publishing, 1972.

12. R.J. Millington and J.M. Quirk, “Permeability of Porous Solids,” Trans. Faraday
Soc., vol. 57, pp. 1200–1207, 1961.

13. I. Langmuir, “Chemical Reactions at Low Temperatures,” J. Amer. Chem. Soc.,

vol. 37, 1915.

242 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Theory for the Electrophoretic
T r a ns po r t Interface
The Electrophoretic Transport Interface models transport of charged and uncharged
species, and in addition sets up a charge balance equation for the electrolyte potential.

The species concentrations are denoted, ci (SI unit: mol/m3), and the potential, φ l
(SI unit: V).

The species are transported by diffusion, migration, and (optionally) convection

according the Nernst-Planck set of equations. The total flux of species i is denoted Ni
(SI unit: mol/(m2·s)) according to

N i = – D i ∇c i – z i u m, i Fc i ∇φ l + uc i = J i + uc i (4-34)

where Di (m2/s) is the diffusion coefficient, zi (1) the corresponding charge, um,i (SI
unit: s·mol/kg) the mobility and u (SI unit: m/s) the velocity vector. Ji denotes the
molar flux relative to the convective transport (SI unit: mol/(m2·s)). For a detailed
description of the theory of these equations and the different boundary conditions, see
Theory for the Transport of Diluted Species Interface.

CHARGE BALANCE EQUATION

2
The current vector, il (A/m ), is defined as

il =  zi Ni (4-35)
i

where the summation is made over all species in the electrolyte.

The governing equation for the electrolyte potential is

∇ ⋅ il = Ql (4-36)

where Ql (A/m3) is the electrolyte current source stemming from, for example,
porous electrode reactions. For non-porous electrode domains this source term is
usually zero.

PROTON AND HYDROXIDE CONCENTRATIONS AND ELECTRONEUTRALITY

Assuming the total number of species to be N+2, the assumption of electroneutrality is

THEORY FOR THE ELECTROPHORETIC TRANSPORT INTERFACE | 243

 N+2

 zi ci = 0 (4-37)
i=1

In water-based systems the species H+ and OH- are always present. The auto
ionization reaction for water is

+ -
H 2 O ↔ H + OH (4-38)

This reaction is fast, following the equilibrium relation

2 –6
c H + c OH - = K w × 1 mol dm (4-39)

– 14
where K w ≈ 10 .

Now, the electroneutrality condition, including the two additional species H+ and
OH-, reads

c H + – c OH- +  zi ci = 0 (4-40)
i=1

Combining these two equations results in the following algebraic expressions for the
concentrations of H+ and OH-.

2
Σ Σ 2 –6
c H + = – --- + ------ + K w × 1 mol dm (4-41)
2 4

and

2
Σ Σ 2 –6
c OH - = --- + ------ + K w × 1 mol dm (4-42)
2 4

where

Σ =  zi ci (4-43)
i=1

MASS BALANCE EQUATIONS FOR DISSOCIATION SPECIES

Assume a set of species Si describing k dissociation steps from

244 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

 + z +k–1
z +k z +k–1 + [ H ] [ S k0– 1 ]
S k0 ↔ S k0– 1 +H K a, 1 = ----------------------------------------
z0 + k
(4-44)
[ Sk ]

to

+ z
z +1 z + [ H ] [ S 00 ]
S k0 ↔ S 00 + H K a, k = -------------------------
z +1
- (4-45)
[ S 10 ]

where z0 is the charge (valence) of species S0 (which has no dissociable protons) and
Ka,j is the acid (equilibrium) constant of the jth dissociation reaction. The brackets [ ]
here represents the species activity. The charge of each species is always deductible from
the index i according to z0+i and will be dropped from now on.

If the proton activity is known, any species Sm may be expressed using any other species
Sl according to

m–l
[H] [ Sl ]
[ S m ] = -------------------------------------
k–l
(4-46)

∏ K a, j
j = k–m+1

if m>l and

k–m
m–l
[ Sm ] = [ H ] [ Sl ] ∏ K a, j
j = k–l+1
(4-47)

if l>m.

Setting m=i and denoting the flux of species i by Ni using equation Equation 4-34,
the mass balance equation for the concentration ci of each subspecies i in the
dissociation chain is

δc
-------i + ∇ ⋅ N i = R eq, i, k – i – R eq, i, k – i + 1 + R i (4-48)
δt

where Req,i,j is the reaction source stemming from the jth dissociation step (with
Req,i,k+1=0), and Ri any additional reaction sources.

The reaction source contributions from the dissociation steps are generally not known,
but may be canceled by taking the sum of all mass balance equations, resulting in

THEORY FOR THE ELECTROPHORETIC TRANSPORT INTERFACE | 245

 k k
δc i
 ------ 
 -
 δt + ∇ ⋅ N i =  Ri (4-49)
i=0 i=0

AVERAGE IONIZATION FORMULATION FOR LARGE MOLECULES

Large protein molecules are typically subject to a large number of dissociation steps.

As an alternative way to a long chain of dissociation steps for describing protein

transport, one can instead formulate the protein transport based on the average
number of protons ν (1) removed from the molecule. ν is typically provided as a
function of pH, based on experimental data. The average charge of the species then is
z = z 0 – ν , so that the flux of the species is written as:

N i = – D∇c i – zu m Fc i ∇φ l + uc i (4-50)

and similarly the addition to the charge neutrality condition is zc i .

When considering the contribution to the current and the charge balance equation one
2 2
needs to take into account that the squared average charge, z = ( z 0 – ν ) , is not
2 2 2 2 2 2
equal to the “average squared charge”, z = z 0 + 2z 0 ν + ν = z – ν + ν (Ref. 1).

The addition to the current density vector is

2
i l = … – F ( zD i ∇c i + z u m c i ∇φ l ) (4-51)

The average number of protons removed from the proton typically depends on the
pH. If the average number of removed protons depend only on the pH, the averaged
squared number of protons removed can be written as

2 d ν ν2
ν = – cH+ + (4-52)
d c H+

And from this one can derive the average squared charge according to

2 d ν z2 d z z2
z = – c H+ + = – cH+ + (4-53)
d cH+ d cH+

DIFFUSIVITY-MOBILITY RELATIONS
The Stokes radius r of a molecule is related to the diffusivity according to

kT
r = --------------- (4-54)
6πμD

246 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

where is the μ (Pa·s) is the dynamic viscosity and k the Boltzmann constant.

For small molecules, one frequently uses the Nernst-Einstein relation between the
diffusivity and the mobility

D
u m = -------- (4-55)
RT

For larger molecules, such as proteins, the mobility may instead be calculated based on
the Debye-Hückel-Henry expression (Ref. 2 ) according to

ef ( κr ) Df ( κr )
u m = ------------------------------------ = ------------------------------ (4-56)
6πμF ( 1 + κr ) RT ( 1 + κr )

where κ (1/m) is the Debye parameter, which depends on the ionic strength of the
solution, is defined for ideal solutions as

2 N
2e N A
 zi ci
2 2
κ = ----------------- (4-57)
εε 0 kT
i=1

where ε is the dielectric constant of the fluid and ε0 the permittivity of free space.
2
( z should be used if available in the formula above when calculating the ionic
strength).

The function f above is based on a sigmoidal function so that it ranges from 1 for
κr = 0 to 1.5 for κr = ∞ . Note that the Debye-Hückel-Henry expression
approaches the Nernst-Einstein mobility as r → 0 .

For larger molecules (macro ions), where the distance between the charges is large
compared to 1/κ, the Linderstrøm-Lang approximation postulates a smaller
contribution of to the ionic strength so that the z-valent ion behaves as a monovalent
ion with a z-fold concentration. For an assemble of N-M smaller molecules and M
macro ions, the Debye parameter then is defined as

N–M N
2e N A  
2
κ = -----------------    abs(z i)c i
2 2
zi ci + (4-58)
εε 0 kT  
 i=1 i = N–M+1 

REFERENCES
1 The Dynamics of Electrophoresis, Mosher, Saville and Thormann, VCH
Verlagsgesellschaft mbH, Weinheim, Germany, 1992.

THEORY FOR THE ELECTROPHORETIC TRANSPORT INTERFACE | 247

 2 Computer Simulation and Experimental Validation of the Electrophoretic
Behavior of Proteins. 2. Model Improvement and Application to Isotachophoresis,
Mosher, Gebauer, Caslavska, and Thormann. Analytical Chemistry, Vol. 64,
pp. 2991–2997, 1992.

248 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

T he o r y f o r t he S u rface R eact i on s
Interface
The Surface Reactions Interface solves for an arbitrary number of surface
concentrations, cs,i (SI unit: mol/m2), referring to species adsorbed on a reactive
surface, and an arbitrary number of bulk concentrations cb,k (SI unit: mol/m3),
referring to the species in the solid material that constitutes the bulk of the reactive
surface.

In this section:

• Governing Equations for the Surface Concentrations

• Governing Equations for the Bulk Concentrations
• ODE-Formulations for Surface Concentrations
• Surface Reaction Equations on Deforming Geometries
• Reference for the Surface Reactions Interface

Governing Equations for the Surface Concentrations

Transport of adsorbed species occurs in the tangential direction along the surface. The
Surface Reactions interface models the tangential flux in the surface dimension, the
surface molar flux, Nt,i (SI unit: mol/(m·s)) (the subscript t refers to the tangential
direction), as governed by diffusion according to Fick’s law:

N t, i = – D s, i ∇ t c s, i

where Ds,i (SI unit: m2/s) is the surface diffusion coefficient for species i.

The governing equation for the surface concentrations is written as:

∂c s, i
= – ∇ t ⋅ N t, i + R s , i (4-59)
∂t

where Rs,i (SI unit: mol/(m2·s)) is the sum of all sources due to surface reactions and
adsorption/desorption phenomena.

Of frequent interest for surface reaction kinetics are the fractional surface coverages, θi
(dimensionless), of the species (with index i).

THEORY FOR THE SURFACE REACTIONS INTERFACE | 249

 Writing the density of sites of the surface as Γ s (SI unit: mol/m2) and the site
occupancy number for each species as σi (dimensionless), the surface coverages can be
calculated from:

σ i c s, i
θ i = --------------
Γs

(The site occupancy number accounts for the situation when a large species covers
more than one site on the surface.)

For the case of monolayer adsorption, the sum of all fractional coverages of free and
adsorbed sites is unity, and hence the fraction of free sites on the surface, θ*, can be
calculated from:

θ* = 1 –  θi
i

Governing Equations for the Bulk Concentrations

BULK SPECIES RATES AND GROWTH VELOCITY

The reaction rate for a bulk species of index k, being added to the bulk due to surface
reactions is defined as Rb,k (SI unit: mol/(s·m2)).

The reaction rate in mass basis, rb,k (SI unit: kg/(s·m2)) for species k, is given by:

r k = M k R b, k

with Mk (SI unit: kg/mol) being the molar mass of the species.

Based on this, the species contribution to the bulk growth velocity, vk (SI unit: m/s),
is given by:

r b, k
v b, k = ----------
ρk

where ρk is the species density (SI unit: kg/m3).

TOTAL RATES AND VELOCITY

To get the corresponding total values, a summation for all bulk species is made
according to:

250 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

 R b, tot =  R b, k
k

r b, tot =  r b, k
k

v b, tot =  v b, k
k

FRACTIONAL RATES AND VELOCITY

The fractional deposition rates are calculated by:

R b, k
R b, frac, k = ---------------
R b, tot

r b, k
r b, frac, k = -------------
r b, tot

v b, k
v b, frac, k = --------------
v b, tot

The fractional deposition rates can be used as measures of the local

fractional composition in a deposited layer at a certain thickness or time.

ACCUMULATED BULK QUANTITIES

By solving for the bulk species concentrations for each time step, the accumulated mass
and thickness changes of the bulk material can be calculated.

The bulk concentration, cb,k (SI unit: mol/m2), for species k is governed by the
equation:

∂c b, k
= R b, k (4-60)
∂t

The bulk concentration in mass basis, mb,k (SI unit: kg/m2) for a species k, can be
derived from:

m b, k = M k c b, k

THEORY FOR THE SURFACE REACTIONS INTERFACE | 251

 leading to the bulk thickness sb,k (SI unit: m) of species k according to:

m b, k
s b, k = -------------
ρk

TOTAL BULK QUANTITIES

The total bulk concentration is calculated according to:

c b, tot =  c b, k
k

The deposited total mass, mb,tot (SI unit: kg/m2) is

m b, tot =  m b, k
k

and the total bulk thickness, stot (SI unit: m) is

s b, tot =  sk
k

FRACTIONAL QUANTITIES
The fractional bulk concentration, bulk mass, and thickness (all dimensionless) are
calculated according to:

c b, k
c b, frac, k = -------------
c b, tot

m b, k
m b, frac, k = ----------------
m b, tot

s b, k
s b, frac, k = -------------
s b, tot

ODE-Formulations for Surface Concentrations

The surface of a 1D geometry has a 0 dimension, hence no surface transport can be
modeled and the governing equation is reduced to an ODE:

252 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

 ∂c s, i
= R s, i
∂t

Surface Reaction Equations on Deforming Geometries

If a Surface Reaction interface is used in conjunction with a Deformed Geometry or a
Moving Mesh (ale) interface the boundary concentration can either be assumed to be
transported with the deforming geometry (moving mesh), with no compensation for
the stretching (the Compensate for boundary stretching check box is not selected), or
the species can be assumed to “float” on the mesh (the Compensate for boundary
stretching check box is selected, which is the default). In the latter case the following
is assumed in regards to the coupling between the surface species and bulk species and
the mesh movement:

• Expansion or contraction of the boundary dilutes or increases concentration of the

species, respectively, so that the surface integral (in spatial coordinates) of the species
is kept constant.
• Tangential mesh movement has no impact on the local concentration in spatial
coordinates, that is, the tangential transport of surface and bulk species does not
move with the mesh in the tangential direction.

In order to comply with the additional contributions to the mass balance, equations
are added. First, the following terms are added to the right-hand side of Equation 4-59
and Equation 4-60, respectively.

– c s, i ∂ ln ∂ A
∂t

– c b, k ∂ ln ∂ A
∂t

where ∂A is the infinitesimal mesh area segment (area scale factor). The above terms
account for the concentration change due to a fractional area change.

Second, the resulting unwanted tangential convection, imposed by the mesh

movement, is compensated for by the adding following terms to the right-hand side of
Equation 4-59 and Equation 4-60, respectively:

∇ t ⋅ ( c s, i v t, mesh )

∇ t ⋅ ( c b, k v t, mesh )

THEORY FOR THE SURFACE REACTIONS INTERFACE | 253

 where vt,mesh is the mesh velocity in the tangential direction.

This convectional term needs often to be stabilized using methods such as streamline
diffusion or isotropic diffusion.

Reference for the Surface Reactions Interface

1. R.J. Kee, M.E. Coltrin, and P. Glarborg, Chemically Reacting Flow, chapter 11,
John Wiley & Sons, 2003.

254 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

Theory for the Coupling of Mass
Transport to Electrochemical
Reactions
When relating the species fluxes at an electrode surface to the electrical currents, the
general chemical reaction formula

 νox Sox + ne  νred Sred

-
⇔
ox red

is used to define the stoichiometric coefficients, νi, with νi being positive (νred) for
products and negative (νox) for the reactants in a reduction reaction. The number of
participating electrons, n, is always positive.

In this section:

• Molar Sources and Sinks

• Mass Sources and Sinks

Molar Sources and Sinks

The molar species fluxes, Ni (SI unit: mol/(m2·s)), perpendicular to an
electrode-electrolyte interface are calculated by summing all the flux contributions
from the electrode reactions, of index m, according to Faraday’s law:

ν i, m i m
Ni =  -----------------
nm F
-
m

where im is the local current density (SI unit: A/m2) of the electrochemical reaction,
nm the number of participating electrons and F (SI unit: C/mol) is Faraday’s
constant.

The molar species flux, Ni, is obtained from normal component of the molar species
flux vector over the electrode-electrolyte interface:

Ni = Ni ⋅ n

where n is the normal vector of the boundary pointing into the domain.

THEORY FOR THE COUPLING OF MASS TRANSPORT TO ELECTROCHEMICAL REACTIONS | 255

 For a porous electrode, the electrochemical reactions result in species source terms
calculated from:

ν i, m i m
R i, molar = –  av, m -----------------
nm F
-
m

where av,m, (SI unit: m2/m3) is the specific surface area.

Mass Sources and Sinks

To compute the mass flux of a species, ni (SI unit: kg/(m2·s)), the molar flux is
multiplied by the molar mass, Mi (SI unit: kg/mol), resulting in

ni ⋅ n = Mi Ni

for a mass flux boundary, and

R i, mass = M i R i, molar

for a porous source term.

256 | CHAPTER 4: CHEMICAL SPECIES TRANSPORT INTERFACES

 5

Fluid Flow Interfaces

This chapter describes the physics interfaces found under the Fluid Flow>Porous
Media and Subsurface Flow branch ( ). The chapter summarizes each physics
interface including the different fields, material properties, and boundary
conditions associated with them, and suggests how and when to apply it.

In this chapter:

• The Darcy’s Law Interface

• The Free and Porous Media Flow Interface
• The Brinkman Equations Interface
• Theory for the Darcy’s Law Interface
• Theory for the Free and Porous Media Flow Interface
• Theory for the Brinkman Equations Interface
• Theory for the Coupling of Fluid Flow to Electrochemical Reactions

257
 The Darcy’s Law Interface
The Darcy’s Law (dl) interface ( ), found under the Porous Media and Subsurface Flow
branch ( ) when adding a physics interface, is used to simulate fluid flow through
interstices in a porous medium. It can be used to model low-velocity flows or media
where the permeability and porosity are very small, and for which the pressure gradient
is the major driving force and the flow is mostly influenced by the frictional resistance
within the pores. Set up multiple Darcy's Law interfaces to model multiphase flows
involving more than one mobile phase. The Darcy’s Law interface can be used for
stationary and time-dependent analyses.

The main feature is the Fluid and Matrix Properties node, which provides an interface
for defining the fluid material along with the porous medium properties.

When this physics interface is added, the following default nodes are also added in the
Model Builder — Fluid and Matrix Properties, No Flow (the default boundary condition),
and Initial Values. Then, from the Physics toolbar, add other nodes that implement, for
example, boundary conditions and mass sources. You can also right-click Darcy's Law
to select physics features from the context menu.

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is dl.

PHYSICAL MODEL
Enter a Reference pressure level pref (SI unit: Pa). The default value is 1[atm].

DEPENDENT VARIABLES
The dependent variable (field variable) is the Pressure. The name can be changed but
the names of fields and dependent variables must be unique within a model.

258 | CHAPTER 5: FLUID FLOW INTERFACES

DISCRETIZATION
You can choose the order of the shape functions used for the pressure variable solved
by the Darcy’s Law interface. The default shape functions are Quadratic Lagrange.

To display all settings available in this section, click the Show button ( ) and select
Advanced Physics Options.

The Compute boundary fluxes check box is not activated by default. When this option
is selected, the solver computes variables storing accurate boundary fluxes from each
boundary into the adjacent domain.

If the check box is cleared, the COMSOL Multiphysics software instead computes the
flux variables from the dependent variables using extrapolation, which is less accurate
in post processing results, but does not create extra dependent variables on the
boundaries for the fluxes.

Also the Apply smoothing to boundary fluxes check box is available if the previous check
box is checked. The smoothing can provide a better behaved flux value close to
singularities.

For details about the boundary fluxes settings, see Computing Accurate Fluxes in the
COMSOL Multiphysics Reference Manual.

The Value type when using splitting of complex variables setting should in most pure
mass transport problems be set to Real which is the default. It makes sure that the
dependent variable does not get affected by small imaginary contributions, which can
occur, for example, when combining a Time Dependent or Stationary study with a
frequency-domain study. For more information, see Splitting Complex-Valued
Variables in the COMSOL Multiphysics Reference Manual.

• Domain, Boundary, Edge, Point, and Pair Nodes for the Darcy’s Law
Interface
• Theory for the Darcy’s Law Interface
• Physical Constants in the COMSOL Multiphysics Reference Manual

Domain, Boundary, Edge, Point, and Pair Nodes for the Darcy’s Law
Interface
The Darcy’s Law Interface has the following domain, boundary, edge, point, and pair
nodes, These nodes available from the Physics ribbon toolbar (Windows users), Physics

THE DARCY’S LAW INTERFACE | 259

 context menu (Mac or Linux users), or right-click to access the context menu (all
users).

In general, to add a node, go to the Physics toolbar, no matter what

operating system you are using. Subnodes are available by clicking the
parent node and selecting it from the Attributes menu.

For axisymmetric components, COMSOL Multiphysics takes the axial

symmetry boundaries (at r = 0) into account and automatically adds an
Axial Symmetry node that is valid on the axial symmetry boundaries only.

In the COMSOL Multiphysics Reference Manual see Table 2-3 for links
to common sections and Table 2-4 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

DOMAIN

• Fluid and Matrix Properties • Initial Values

• Mass Source

BOUNDARY, EDGE, AND POINT

The following nodes (listed in alphabetical order) are available on exterior boundaries:

The relevant physics interface condition at interior boundaries is continuity:

n ⋅ ( ρ1 u1 –ρ2 u2 ) = 0

The continuity boundary condition ensures that the pressure and mass flux are
continuous. In addition, the Pressure boundary condition is available on interior
boundaries.

260 | CHAPTER 5: FLUID FLOW INTERFACES

Fluid and Matrix Properties
The Fluid and Matrix Properties node adds the equations for Darcy’s law, Equation 5-1
and Equation 5-2(excluding any mass sources), and contains settings for the fluid
properties and the porous matrix properties such as the effective porosity.

∂ ( ρε ) + ∇ ⋅ ( ρu )
= Qm (5-1)
∂t

κ
u = – --- ∇p (5-2)
μ

FLUID PROPERTIES
Select the Fluid material to use for the fluid properties. Select Domain material (the
default) to use the material defined for the domain. Select another material to use that
material’s properties for the fluid.

Density
The default Density ρ (SI unit: kg/m3) uses values From material based on the Fluid
material selection.

• For User defined enter another value or expression. The default is 0 kg/m3.
• For Ideal gas it uses the ideal gas law to describe the fluid. In this case, specify the
thermodynamics properties. Select a Gas constant type—Specific gas constant Rs (the
default) or Mean molar mass Mn (SI unit: J/(mol·K)). For Mean molar mass the
universal gas constant R = 8.314 J/(mol·K) is used as the built-in physical constant.
For both properties, the defaults use values From material. For User defined enter
another value or expression.

Dynamic Viscosity
Select a Dynamic viscosity μ (SI unit: Pa·s). The default uses values From material as
defined by the Fluid material selected. For User defined the default is 0 Pa·s.

MATRIX PROPERTIES
Select the material to use as porous matrix. Select Domain material from the Porous
material list (the default) to use the material defined for the porous domain. Select
another material to use that material’s properties.

The default Porosity εp (a dimensionless number between 0 and 1) uses the value From
material, defined by the Porous material selected. For User defined the default is 0.

THE DARCY’S LAW INTERFACE | 261

 Select a Permeability model to specify the capacity of the porous material to transmit
flow—Permeability to define the permeability of the porous matrix, or Kozeny-Carman
to define the permeability from the porosity and mean particle diameter.

The default Permeability κ (SI unit: m2) uses the value From material, as defined by the
Porous material selected. For User defined select Isotropic to define a scalar value or
Diagonal, Symmetric, or Anisotropic to define a tensor value and enter another value or
expression in the field or matrix.

For Kozeny-Carman, enter the mean particle diameter dp (SI unit: m), the default value
is 0.5 mm.

Mass Source
The Mass Source node adds a mass source Qm, which appears on the right-hand side of
the Darcy’s Law equation (Equation 5-8, the equation for porosity).

∂ ( ρε ) + ∇ ⋅ ( ρu ) = Q
m (5-3)
∂t

MASS SOURCE
Enter a value or expression for the Mass source Qm (SI unit: kg/(m3·s)). The default is
0 kg/(m3·s).

Initial Values
The Initial Values node adds an initial value for the pressure that can serve as an initial
condition for a transient simulation or as an initial guess for a nonlinear solver.

INITIAL VALUES
Enter a value or expression for the initial value of the Pressure p (SI unit: Pa). The
default value is 0 Pa.

Porous Electrode Coupling

Use the Porous Electrode Coupling node to define a mass source based on the volumetric
current densities of one or multiple Porous Electrode Reaction nodes in an
Electrochemistry interface.

262 | CHAPTER 5: FLUID FLOW INTERFACES

The source (or sink) is proportional to the Molar mass (kg/mol) of the reacting species,
the current densities and the stoichiometric coefficients according to Faraday’s law as
defined by summation over the Reaction Coefficient subnodes.

SPECIES
Based on the number of species required for the model, use the Add ( ) and
Delete ) buttons under the table to add or remove Species. Then enter a value for
the Molar mass (kg/mol) in the applicable rows for each species.

The setting in the table will determine the number of available fields for entering the
stoichiometric coefficients of the Reaction Coefficient subnodes.

Electrode Surface Coupling

Use the Electrode Surface Coupling node to define a combined wall and inflow/outflow
boundary condition based on current densities of one or multiple Electrode Reaction
nodes in an Electrochemistry interface.

The flow is proportional to the Molar mass (kg/mol) of the reacting species, the current
densities and the stoichiometric coefficients according to Faraday’s law as defined by
summation over the Reaction Coefficient subnodes.

SPECIES
Based on the number of species required for the model, use the Add ( ) and
Delete ) buttons under the table to add or remove Species. Then enter a value for
the Molar mass (kg/mol) in the applicable rows for each species.

The setting in the table will determine the number of available field for entering the
stoichiometric coefficients of the Reaction Coefficient subnodes.

Pressure
Use the Pressure node to specify the pressure on a boundary. In many cases the
distribution of pressure is known, giving a Dirichlet condition p = p0 where p0 is a
known pressure given as a number, a distribution, or an expression involving time, t,
for example.

PRESSURE
Enter a value or expression for the Pressure p0(SI unit: Pa). Enter a relative pressure
value in p0 (SI unit: Pa).

THE DARCY’S LAW INTERFACE | 263

 CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.

Mass Flux
Use the Mass Flux node to specify the mass flux into or out of the model domain
through some of its boundaries. It is often possible to determine the mass flux from
the pumping rate or from measurements. With this boundary condition, positive
values correspond to flow into the model domain:

κ
n ⋅ ρ --- ∇p = N 0
μ

where N0 is a value or expression for the specified inward (or outward) Darcy flux.

For modeling mass flux from very thin objects add a Line Mass Source or a Point Mass
Source node.

The Line Mass Source node adds mass flow originating from a tube of infinitely small
radius. It is available for edges in 3D geometries or points in 2D and 2D axisymmetric
geometries.

The Point Mass Source node models mass flow originating from an infinitely small
sphere centered around a point. It is available for points in 3D geometries.

MASS FLUX
Enter a value or expression for the Inward mass flux N0. A positive value of N0
represents an inward mass flux whereas a negative value represents an outward mass
flux. The units are based on the geometric entity: Boundaries: (SI unit: kg/(m2·s)),
Edges (SI unit: kg/(m·s), and Points (SI unit: kg/s)).

Inlet
The Inlet node adds a boundary condition for the inflow (or outflow) perpendicular
(normal) to the boundary:

κ
n ⋅ ρ --- ∇p = ρU 0
μ

where U0 is a value or expression for the specified inward (or outward) Darcy velocity.
A positive value of the velocity U0 corresponds to flow into the model domain whereas
a negative value represents an outflow.

264 | CHAPTER 5: FLUID FLOW INTERFACES

INLET
Enter a value or expression for the Normal inflow velocity U0 (SI unit: m/s). A positive
value of U0 represents an inflow velocity. A negative value represents an outflow
velocity.

Symmetry
The Symmetry node describes a symmetry boundary. The following condition
implements the symmetry condition on an axis or a flow divide:

κ
n ⋅ --- ∇p = 0
μ

For axisymmetric components, COMSOL Multiphysics takes the axial symmetry

boundaries (at r = 0) into account and automatically adds an Axial Symmetry node that
is valid on the axial symmetry boundaries only.

No Flow
The No Flow node is the default boundary condition stating that there is no flow across
impervious boundaries. The mathematical formulation is:

κ
n ⋅ ρ --- ∇p = 0
μ

where n is the vector normal to the boundary.

Flux Discontinuity
Use the Flux Discontinuity node to specify a mass flux discontinuity through an interior
boundary. The condition is represented by the following equation:

– n ⋅ ( ρu 1 – ρ u 2 ) = N 0

In this equation, n is the vector normal (perpendicular) to the interior boundary, ρ is

the fluid density, u1 and u2 are the Darcy velocities in the adjacent domains (as defined
in Equation 5-7) and N0 is a specified value or expression for the flux discontinuity.

κ
u = – --- ∇p (5-4)
μ

THE DARCY’S LAW INTERFACE | 265

 For this boundary condition, a positive value of N0 corresponds to a flow discontinuity
in the opposite direction to the normal vector of the interior boundary.

MASS FLUX
Enter a value or expression for the Inward mass flux N0 (SI unit: kg/(m2·s)). A positive
value of N0 represents a mass flux discontinuity in the opposite direction to the normal
vector of the interior boundary.

Outlet
The Outlet node adds a boundary condition for the outflow (or inflow) perpendicular
(normal) to the boundary:

κ
– n ⋅ ρ --- ∇p = ρU 0
μ

where U0 is a specified value or expression for the outward (or inward) Darcy velocity.
A positive value of the velocity U0 corresponds to flow out of the model domain
whereas a negative value represents an inflow.

OUTLET
Enter a value or expression for the Normal outflow velocity U0 (SI unit: m/s). A positive
value of U0 represents an outflow velocity whereas a negative value represents an
inflow velocity.

Cross Section
Use this node with 1D components to model domains with another cross sectional
area than the global one that is used in the interface Physical Model section. In 1D
geometries, the pressure is assumed to be constant in the radial direction, and Darcy’s
Law accounts for that.

CROSS SECTION
Enter values for the Cross-sectional area Ac to set the cross section of the domain in the
plane perpendicular to the 1D geometry.

Thickness
Use this node with 2D and 1D axisymmetric components to model domains with
another thickness than the overall thickness that is specified in the interface Physical

266 | CHAPTER 5: FLUID FLOW INTERFACES

Model section. In 2D geometries, the pressure is assumed to be constant in the
out-of-plane direction (z direction with default spatial coordinate names). In 1D
axisymmetric geometries the thickness represents the z direction.

THICKNESS
Specify a value for the Thickness dz of the domain in the out-of-plane direction. This
value replaces the overall thickness in the domains that are selected in the Domain
Selection section, and is used to multiply some terms into the heat equation.

THE DARCY’S LAW INTERFACE | 267

 The Free and Porous Media Flow
Interface
The Free and Porous Media Flow (fp) interface ( ), found under the Porous Media and
Subsurface Flow branch ( ) when adding a physics interface, is used to compute fluid
velocity and pressure fields of single-phase flow where free flow is connected to porous
media. The Free and Porous Media Flow interface is used over at least two different
domains: a free channel and a porous medium. The physics interface is well suited for
transitions between slow flow in porous media, governed by the Brinkman equations,
and fast flow in channels described by the Navier-Stokes equations. Fluids with varying
density can be included at Mach numbers below 0.3. Also the viscosity of a fluid can
vary, for example, to describe non-Newtonian fluids. The physics interface can be used
for stationary and time-dependent analyses.

When this physics interface is added, the following default nodes are also added in the
Model Builder— Fluid Properties, Wall, and Initial Values. Then, from the Physics toolbar,
add a Fluid and Matrix Properties node to be used on the domain selection
corresponding to the porous media, or add other nodes that implement, for example,
boundary conditions and volume forces. You can also right-click Free and Porous Media
Flow to select physics features from the context menu.

SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is fp.

PHYSICAL MODEL

Compressibility
By default the physics interface uses the Incompressible flow formulation of the
Navier-Stokes and Brinkman equations to model constant density flow. If required,
select Compressible flow (Ma<0.3) from the Compressibility list, to account for small

268 | CHAPTER 5: FLUID FLOW INTERFACES

variations in the density, typically dependent on the temperature (non-isothermal
flow). For compressible flow modeled with this physics interface, the Mach number
must be below 0.3.

Neglect Inertial Term

Select the Neglect inertial term (Stokes flow) check box if the inertial forces are small
compared to the viscous forces.

Reference Pressure Level

Enter a Reference pressure level pref (SI unit: Pa). The default value is 1[atm].

Reference Temperature
Enter a Reference temperature Tref (SI unit: K). The default value is 293.15[K].

DEPENDENT VARIABLES
The following dependent variables (fields) are defined for this physics interface—the
Velocity field u (SI unit: m/s) and its components, and the Pressure p (SI unit: Pa).

• Domain, Boundary, Point, and Pair Nodes for the Free and Porous
Media Flow Interface
• Theory for the Free and Porous Media Flow Interface

Domain, Boundary, Point, and Pair Nodes for the Free and Porous
Media Flow Interface
The Free and Porous Media Flow Interface has the following domain, boundary,
point, and pair nodes, listed in alphabetical order, available from the Physics ribbon
toolbar (Windows users), Physics context menu (Mac or Linux users), or right-click to
access the context menu (all users).

In general, to add a node, go to the Physics toolbar, no matter what

operating system you are using. Subnodes are available by clicking the
parent node and selecting it from the Attributes menu.

THE FREE AND POROUS MEDIA FLOW INTERFACE | 269

 • Electrode-Electrolyte Interface • Porous Electrode Coupling
Coupling • Fluid and Matrix Properties
• Fluid Properties • Volume Force
• Forchheimer Drag • Wall
• Initial Values
• Mass Source

See the Transport of Diluted Species interface for Porous Electrode

Couplingand Reaction Coefficients.

The following nodes (listed in alphabetical order) are described for the Laminar Flow
interfacein the COMSOL Multiphysics Reference Manual:

• No Viscous Stress • Open Boundary

• Flow Continuity • Periodic Flow Condition
• Inlet • Point Mass Source
• Line Mass Source • Pressure Point Constraint
• Outlet • Symmetry

In the COMSOL Multiphysics Reference Manual see Table 2-3 for links
to common sections and Table 2-4 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Fluid Properties
Use the Fluid Properties node to define the fluid material, density, and dynamic
viscosity.

FLUID PROPERTIES
The default Fluid material uses the Domain material (the material defined for the
domain). Select another material as needed.

270 | CHAPTER 5: FLUID FLOW INTERFACES

The default Density ρ (SI unit: kg/m3) uses values From material based on the Fluid
material selection. For User defined enter another value or expression. The default is
0 kg/m3.

The Dynamic viscosity μ (SI unit: Pa·s) uses values From material based on the Fluid
material selection. For User defined enter another value or expression. The default is
0 Pa·s.

Fluid and Matrix Properties

Use the Fluid and Matrix Properties node to define which domains contain porous
material and to define the porous matrix properties, such as the porosity and
permeability in these domains. The Forchheimer Drag subnode is available from the
context menu (right-click the parent node) or from the Physics toolbar, Attributes
menu.

DOMAIN SELECTION
Choose domains from the Selection list, to solve for porous media flow governed by
the Brinkman equations. In the domains not selected, the Free and Porous Media Flow
interface solves for laminar flow governed by the Navier-Stokes (or Stokes) equations.

POROUS MATRIX PROPERTIES

The default Porous material uses the Domain material (the material defined for the
domain) for the porous matrix. Select another material as needed.

Porosity
The default Porosity εp (a dimensionless number between 0 and 1) uses values From
material as defined by the Porous material selection. For User defined enter another
value or expression. The default is 0.

In this node you specify the porosity εp, whereas in other nodes the
volume fraction of solid material θp=1- εp is required instead. See Porous
Medium in the Heat Transfer Module User’s Guide for an example.

Permeability
The default Permeability κbr (SI unit: m2) uses values From material as defined by the
Porous material selection. For User defined select Isotropic, Diagonal, Symmetric, or
Anisotropic from the list and then enter other values or expressions. The components
of a permeability in the case that it is a tensor (κxx, κyy, and so on, representing an

THE FREE AND POROUS MEDIA FLOW INTERFACE | 271

 anisotropic permeability) are available as fp.kappaxx, fp.kappayy, and so on (using
the default name fp). The default is 0 m2.

Source Term
Enter a value or expression for an optional mass source (or sink) Source term Qbr (SI
unit: kg/(m3·s)). This term accounts for mass deposit and mass creation within
domains. The physics interface assumes that the mass exchange occurs at zero velocity.

Volume Force
The Volume Force node specifies the force F on the right-hand side of the
Navier-Stokes or Brinkman equations, depending on whether the Porous Matrix
Properties node is active for the domain. Use it, for example, to incorporate the effects
of gravity in a model.

VOLUME FORCE
Enter the components of the Volume force F (SI unit: N/m3).

Forchheimer Drag
The Forchheimer Drag subnode is available from the context menu (right-click the Fluid
and Matrix Properties parent node) or from the Physics toolbar, Attributes menu. It can
be used on the domain selection that corresponds to the porous medium. For the
Brinkman equations the drag of the fluid on the porous matrix is proportional to the
flow velocity, in the same way as for Darcy’s law. Add a Forchheimer drag, proportional
to the square of the fluid velocity, as needed.

FORCHHEIMER DRAG
Enter a value for the Forchheimer coefficient βF (SI unit: kg/m4).

Porous Electrode Coupling

Use the Porous Electrode Coupling node to define a mass source based on the volumetric
current densities of one or multiple Porous Electrode Reaction nodes in an
Electrochemistry interface.

The source (or sink) is proportional to the Molar mass (kg/mol) of the reacting species,
the current densities and the stoichiometric coefficients according to Faraday’s law as
defined by summation over the Reaction Coefficient subnodes.

272 | CHAPTER 5: FLUID FLOW INTERFACES

SPECIES
Based on the number of species required for the model, use the Add ( ) and
Delete ) buttons under the table to add or remove Species. Then enter a value for
the Molar mass (kg/mol) in the applicable rows for each species.

The setting in the table will determine the number of available fields for entering the
stoichiometric coefficients of the Reaction Coefficient subnodes.

Initial Values
The Initial Values node adds initial values for the velocity field and the pressure that can
serve as an initial condition for a transient simulation or as an initial guess for a
nonlinear solver.

INITIAL VALUES
Enter initial values or expressions for the Velocity field u (SI unit: m/s) and for the
Pressure p (SI unit: Pa). The default values are 0 m/s and 0 Pa, respectively.

Electrode-Electrolyte Interface Coupling

Use the Electrode-Electrolyte Interface Coupling node to define a combined wall and
inflow/outflow boundary condition based on current densities of one or multiple
Electrode Reaction nodes in an Electrochemistry interface.

The flow is proportional to the Molar mass (kg/mol) of the reacting species, the current
densities and the stoichiometric coefficients according to Faraday’s law as defined by
summation over the Reaction Coefficient subnodes.

TANGENTIAL VELOCITY CONDITION

For information about this section, see the Wall node. No slip is the default, but Slip
may in some cases be a more applicable, for instance if a gas diffusion electrode is
modeled as a boundary condition.

SPECIES
Based on the number of species required for the model, use the Add ( ) and
Delete ) buttons under the table to add or remove Species. Then enter a value for
the Molar mass (kg/mol) in the applicable rows for each species.

The setting in the table will determine the number of available field for entering the
stoichiometric coefficients of the Reaction Coefficient subnodes.

THE FREE AND POROUS MEDIA FLOW INTERFACE | 273

 Wall
The Wall node includes a set of boundary conditions describing fluid-flow conditions
at stationary, moving, and leaking walls.

BOUNDARY CONDITION
Select a Boundary condition for the wall.

• No Slip1 • Leaking Wall

• Slip

No Slip
No slip is the default boundary condition for a stationary solid wall for laminar flow
(and SST, Low Re k-ε, Algebraic yPlus, L-VEL, and Spalart-Allmaras turbulence
models). The condition prescribes u = 0; that is, the fluid at the wall is not moving.

Slip
The Slip option prescribes a no-penetration condition, u·n=0. It is implicitly assumed
that there are no viscous effects at the slip wall and hence, no boundary layer develops.
From a modeling point of view, this can be a reasonable approximation if the main
effect of the wall is to prevent fluid from leaving the domain.

Leaking Wall
This boundary condition may be used to simulate a wall where fluid is leaking into or
leaving the domain with the velocity u = ul through a perforated wall. The
components of the Fluid velocity ul on the leaking wall should be specified.

CONSTRAINT SETTINGS
This section is displayed by clicking the Show button ( ) and selecting Advanced
Physics Options.

• The Moving Mesh Interface in the COMSOL Multiphysics Reference

Manual

274 | CHAPTER 5: FLUID FLOW INTERFACES

The Brinkman Equations Interface
The Brinkman Equations (br) interface ( ), found under the Porous Media and
Subsurface Flow branch ( ) when adding a physics interface, is used to compute fluid
velocity and pressure fields of single-phase flow in porous media in the laminar flow
regime. The physics interface extends Darcy’s law to describe the dissipation of the
kinetic energy by viscous shear, similar to the Navier-Stokes equations. Fluids with
varying density can be included at Mach numbers below 0.3. Also the viscosity of a
fluid can vary, for example, to describe non-Newtonian fluids. To simplify the
equations, select the Stokes-Brinkman flow feature to reduce the dependence on
inertial effects when the Reynolds number is significantly less than 1. The physics
interface can be used for stationary and time-dependent analyses.

The main node is the Fluid and Matrix Properties feature, which adds the Brinkman
equations and provides an interface for defining the fluid material and the porous
matrix.

When this physics interface is added, the following default nodes are also added in the
Model Builder — Fluid and Matrix Properties, Wall (the default boundary type, using No
slip as the default boundary condition), and Initial Values. Then, from the Physics
toolbar, add other nodes that implement, for example, boundary conditions and
volume forces. You can also right-click Brinkman Equations to select physics features
from the context menu.

The boundary conditions are essentially the same as for the Laminar Flow interface.
Differences exist for the following boundary types: Outlet, Symmetry, Open
Boundary, and Boundary Stress where the viscous part of the stress is divided by the
porosity to appear as

1-  T 2 
---- μ ( ∇u + ( ∇u ) ) – --- μ ( ∇ ⋅ u )I 
ε p  3 

In the COMSOL Multiphysics Reference Manual see Table 2-3 for links to common
sections such as Discretization, Consistent Stabilization, and Inconsistent Stabilization,
and Advanced Settings sections, all accessed by clicking the Show button ( ) and
choosing the applicable option. You can also search for information: press F1 to open
the Help window or Ctrl+F1 to open the Documentation window.

THE BRINKMAN EQUATIONS INTERFACE | 275

 SETTINGS
The Label is the default physics interface name.

The Name is used primarily as a scope prefix for variables defined by the physics
interface. Refer to such physics interface variables in expressions using the pattern
<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers, and
underscores (_) are permitted in the Name field. The first character must be a letter.

The default Name (for the first physics interface in the model) is br.

PHYSICAL MODEL
This node specifies the properties of the Brinkman Equations interface, which describe
the overall type of fluid flow model.

Compressibility
By default the physics interface uses the Incompressible flow formulation of the
Brinkman equations to model constant density flow. Alternatively, select Compressible
flow (Ma<0.3) from the Compressibility list if there are small variations in the density,
typically dependent on the temperature (nonisothermal flow). For compressible flow
modeled with the Brinkman Equations interface, the Mach number must be below
0.3.

Neglect Inertial Term (Stokes-Brinkman Flow)

The Neglect inertial term (Stokes-Brinkman) check box is selected by default to model
flow at very low Reynolds numbers for which the inertial term can be neglected in the
Brinkman equations. This results in the linear Stokes-Brinkman equations.

Enable porous media domains

The Enable porous media domains check box is selected by default to solve Brinkman
equations in porous domains.

Reference Pressure Level

Enter a Reference pressure level pref (SI unit: Pa). The default value is 1[atm].

DEPENDENT VARIABLES
The following dependent variables (fields) are defined for this physics interface — the
Velocity field u (SI unit: m/s) and its components, and the Pressure p (SI unit: Pa).

ADVANCED SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.
Normally these settings do not need to be changed.

276 | CHAPTER 5: FLUID FLOW INTERFACES

The Use pseudo time stepping for stationary equation form option adds pseudo time
derivatives to the equation when the Stationary equation form is used in order to speed
up convergence. When selected, a CFL number expression should also be defined. For
the default Automatic option, the local CFL number (from the Courant–Friedrichs–
Lewy condition) is determined by a PID regulator.

• Domain, Boundary, Point, and Pair Nodes for the Brinkman Equations
Interface
• Theory for the Brinkman Equations Interface

In the COMSOL Multiphysics Reference Manual:

• Pseudo Time Stepping for Laminar Flow Models and Pseudo Time
Stepping
• Numerical Stability — Stabilization Techniques for Fluid Flow
• Discontinuous Galerkin Formulation

Domain, Boundary, Point, and Pair Nodes for the Brinkman

Equations Interface
The Brinkman Equations Interface has the following domain, boundary, point, and
pair nodes, listed in alphabetical order, available from the Physics ribbon toolbar
(Windows users), Physics context menu (Mac or Linux users), or right-click to access
the context menu (all users).

In general, to add a node, go to the Physics toolbar, no matter what

operating system you are using. Subnodes are available by clicking the
parent node and selecting it from the Attributes menu.

These nodes are described in this section:

• Fluid and Matrix Properties • Mass Source

• Forchheimer Drag • Volume Force
• Initial Values • Fluid Properties

THE BRINKMAN EQUATIONS INTERFACE | 277

 The following nodes (listed in alphabetical order) are described for the Laminar Flow
interface in the COMSOL Multiphysics Reference Manual:

• Flow Continuity • Periodic Flow Condition

• InletLine Mass Source • Point Mass Source
• Boundary Stress • Pressure Point ConstraintSymmetry
• Outlet • Wall
• Open Boundary

In the COMSOL Multiphysics Reference Manual see Table 2-3 for links
to common sections and Table 2-4 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Fluid and Matrix Properties

The Fluid and Matrix Properties node adds the Brinkman equations: Equation 5-10 and
Equation 5-11 (excluding any mass sources), and provides an interface for defining the
properties of the fluid material and the porous matrix The Forchheimer Drag subnode
is available from the context menu (right-click the parent node) or from the Physics
toolbar, Attributes menu.

FLUID PROPERTIES
The default Fluid material uses the Domain material (the material defined for the
domain). Select another material as needed.

Both the default Density ρ (SI unit: kg/m3) and Dynamic viscosity μ (SI unit: Pa·s) use
values From material based on the Fluid material selection. For User defined enter
another value or expression. In this case, the default is 0 kg/m3 for the density and
0 Pa·s for the dynamic viscosity. The dynamic viscosity describes the relationship
between the shear stresses and the shear rate in a fluid. Intuitively, water and air have
a low viscosity, and substances often described as thick, such as oil, have a higher
viscosity. Non-Newtonian fluids have a viscosity that is shear-rate dependent. Examples
of non-Newtonian fluids include yogurt, paper pulp, and polymer suspensions.

278 | CHAPTER 5: FLUID FLOW INTERFACES

POROUS MATRIX PROPERTIES
The default Porous material uses the Domain material (the material defined for the
domain) for the porous matrix. Select another material as needed.

Both the default Porosity εp (a dimensionless number between 0 and 1) and

Permeability κ (SI unit: m2) use values From material as defined by the Porous material
selection. For User defined select Isotropic, Diagonal, Symmetric, or Anisotropic based on
the characteristics of the permeability, and enter another value or expression. The
components of a permeability in the case that it is a tensor (κxx, κyy, and so on,
representing an anisotropic permeability) are available as br.kappaxx, br.kappayy,
and so on (using the default name br).

Forchheimer Drag
The Forchheimer Drag subnode is available from the context menu (right-click the Fluid
and Matrix Properties parent node) or from the Physics toolbar, Attributes menu.
While the drag of the fluid on the porous matrix in the basic Brinkman equations is
proportional to the flow velocity, (Darcy’s law drag), the Forchheimer drag is
proportional to the square of the fluid velocity. The latter term accounts for an inertial
turbulent drag effect that comes into play for fast flows through large pores. Adding
the Forchheimer term takes into account all drag contributions that the Ergun
equation covers.

FORCHHEIMER DRAG
Enter a value for the Forchheimer coefficient βF (SI unit: kg/m4). The default is 0 kg/
m4.

Mass Source
The Mass Source node adds a mass source (or mass sink) Qbr to the right-hand side of
the continuity equation: Equation 5-10. This term accounts for mass deposit and/or
mass creation in porous domains. The physics interface assumes that the mass
exchange occurs at zero velocity.

∂ ε
( ρ ) + ∇ ⋅ ( ρu ) = Q br (5-5)
∂t p

DOMAIN SELECTION
Only Porous Matrix domains are available.

THE BRINKMAN EQUATIONS INTERFACE | 279

 MASS SOURCE
Enter a value or expression for the Source term Qbr (SI unit: kg/(m3·s)). The default
is 0 kg/(m3·s).

Volume Force
Use the Volume Force node to specify the force F on the right-hand side of
Equation 5-11. It then acts on each fluid element in the specified domains. A common
application is to include gravity effects.

ρ-  ∂u
+ ( u ⋅ ∇ ) ----- =
---- u
εp  ∂ t εp
(5-6)
1 T 2   –1 Q br
–∇ p + ∇ ⋅ ----
- --
-
μ ( ∇u + ( ∇u ) ) – μ ( ∇ ⋅ u )I  –  κ μ + --------
- u + F
ε p  3   ε p2 

VOLUME FORCE
Enter the components of Volume force F (SI unit: N/m3).

Initial Values
The Initial Values node adds initial values for the velocity field and the pressure that can
serve as an initial condition for a transient simulation or as an initial guess for a
nonlinear solver.

INITIAL VALUES
Enter initial values or expressions for the Velocity field u (SI unit: m/s) and the Pressure
p (SI unit: Pa). The default values are 0 m/s and 0 Pa, respectively.

Fluid Properties
The Fluid Properties node adds the momentum and continuity equations to solve for
free flow in nonporous domains. The node also provides an interface for defining the
material properties of the fluid.

MODEL INPUTS
Fluid properties, such as density and viscosity, can be defined through user inputs,
variables or by selecting a material. For the latter option, additional inputs — for
example, temperature or pressure — may be required to define these properties.

280 | CHAPTER 5: FLUID FLOW INTERFACES

Temperature
By default, the single-phase flow interfaces are set to model isothermal flow. Hence,
the Temperature is User defined and defaults to 293.15 K. If a Heat Transfer interface
is included in the component, the temperature may alternatively be selected from this
physics interface. All physics interfaces have their own tags (Name). For example, if a
Heat Transfer in Fluids interface is included in the component, the Temperature (ht)
option is available.

Absolute Pressure
This input appears when a material requires the absolute pressure as a model input.
The absolute pressure is used to evaluate material properties, but it also relates to the
value of the calculated pressure field. There are generally two ways to calculate the
pressure when describing fluid flow: either to solve for the absolute pressure or for a
pressure (often denoted gauge pressure) that relates to the absolute pressure through
a reference pressure.

The choice of pressure variable depends on the system of equations being solved. For
example, in a unidirectional incompressible flow problem, the pressure drop over the
modeled domain is probably many orders of magnitude smaller than the atmospheric
pressure, which, when included, may reduce the stability and convergence properties
of the solver. In other cases, such as when the pressure is part of an expression for the
gas volume or the diffusion coefficients, it may be more convenient to solve for the
absolute pressure.

The default Absolute pressure pA is p+pref where p is the dependent pressure variable
from the Navier-Stokes equations, and pref is from the user input defined at the physics
interface level. When pref is nonzero, the physics interface solves for a gauge pressure.
If the pressure field instead is an absolute pressure field, pref should be set to 0.

The Absolute pressure field can be edited by clicking Make All Model Inputs Editable
( ) and entering the desired value in the input field.

FLUID PROPERTIES
If density variations with respect to pressure are to be included in the computations,
the flow must be set to compressible.

The Dynamic viscosity μ describes the relationship between the shear rate and the shear
stresses in a fluid. Intuitively, water and air have low viscosities, and substances often
described as thick (such as oil) have higher viscosities.

THE BRINKMAN EQUATIONS INTERFACE | 281

 Theory for the Darcy’s Law Interface
The Darcy’s Law Interface theory is described in this section.

In a porous medium, the global transport of momentum by shear stresses in the fluid
is often negligible: the pore walls impede momentum transport between fluid
occupying different pores. In most applications, a detailed description of the resolution
of every pore is not practical. A homogenization of the porous and fluid media into a
single medium is a common alternative approach. Darcy’s law, together with the
continuity equation and equation of state for the pore fluid provides a complete
mathematical model suitable for a variety of applications involving porous media flows
when the pressure gradient is the major driving force.

Darcy’s Law — Equation Formulation

Darcy’s law states that the velocity field is determined by the pressure gradient, the
fluid viscosity, and the structure of the porous medium:

κ
u = – --- ∇p (5-7)
μ

In this equation, κ (SI unit: m2) denotes the permeability of the porous medium, μ
(SI unit: kg/(m·s)) the dynamic viscosity of the fluid, p (SI unit: Pa) the pressure, and
u (SI unit: m/s) the Darcy velocity. The Darcy’s Law interface combines Darcy’s law
with the continuity equation:

∂ ( ρε ) + ∇ ⋅ ( ρu )
= Qm (5-8)
∂t

In the above equation, ρ (SI unit: kg/m3) is the density of the fluid, ε (dimensionless)
is the porosity, and Qm (SI unit: kg/(m3·s)) is a mass source term. Porosity is defined
as the fraction of the control volume that is occupied by pores. Thus, the porosity can
vary from zero for pure solid regions to unity for domains of free flow.

If the Darcy’s Law interface is coupled to an energy balance, then the fluid density can
be a function of the temperature, pressure, and composition (for mixture flows). For
gas flows in porous media, the relation is given by the ideal gas law:

pM
ρ = --------- (5-9)
RT

282 | CHAPTER 5: FLUID FLOW INTERFACES

where R= 8.314 J/(mol·K) is the universal gas constant, M (SI unit: kg/mol) is the
molecular weight of the gas, and T (SI unit: K) is the temperature.

THEORY FOR THE DARCY’S LAW INTERFACE | 283

 Theory for the Free and Porous
Media Flow Interface
The Free and Porous Media Flow Interface uses the Navier-Stokes equations to
describe the flow in open regions, and the Brinkman equations to describe the flow in
porous regions.

The same fields, u and p, are solved for in both the free flow domains and in the porous
domains. This means that the pressure in the free fluid and the pressure in the pores is
continuous over the interface between a free flow domain and a porous domain. It also
means that continuity is enforced between the fluid velocity in the free flow and the
Darcy velocity in the porous domain. This treatment is one of several possible models
for the physics at the interface. Examples of other models can be found in Ref. 1.

The continuity in u and p implies a stress discontinuity at the interface between a

free-flow domain and a porous domain. The difference corresponds to the stress
absorbed by the rigid porous matrix, which is a consequence implicit in the
formulations of the Navier-Stokes and Brinkman equations.

Reference for the Free and Porous Media Flow Interface

1. M.L. Bars and M.G. Worster, “Interfacial Conditions Between a Pure Fluid and a
Porous Medium: Implications for Binary Alloy Solidification,” J. Fluid Mech.,
vol. 550, pp. 149–173, 2006.

284 | CHAPTER 5: FLUID FLOW INTERFACES

Theory for the Brinkman Equations
Interface
The Brinkman Equations Interface theory is described in this section:

• About the Brinkman Equations

• Brinkman Equations Theory
• References for the Brinkman Equations Interface

About the Brinkman Equations

In porous domains, the flow variables and fluid properties are defined at any point
inside the medium by means of averaging of the actual variables and properties over a
certain volume surrounding the point. This control volume must be small compared
to the typical macroscopic dimensions of the problem, but it must be large enough to
contain many pores and solid matrix elements.

Porosity is defined as the fraction of the control volume that is occupied by pores.
Thus, the porosity can vary from zero for pure solid regions to unity for domains of
free flow.

The physical properties of the fluid, such as density and viscosity, are defined as
intrinsic volume averages that correspond to a unit volume of the pores. Defined this
way, they present the relevant physical parameters that can be measured experimentally,
and they are assumed to be continuous with the corresponding parameters in the
adjacent free flow.

The flow velocity is defined as a superficial volume average, and it corresponds to a

unit volume of the medium including both the pores and the matrix. It is sometimes
called the Darcy velocity, defined as the volume flow rate per unit cross section of the
medium. Such a definition makes the velocity field continuous across the boundaries
between porous regions and regions of free flow.

Brinkman Equations Theory

The dependent variables in the Brinkman equations are the Darcy velocity and the
pressure. The flow in porous media is governed by a combination of the continuity
equation and the momentum equation, which together form the Brinkman equations:

THEORY FOR THE BRINKMAN EQUATIONS INTERFACE | 285

 ∂ ( ε ρ ) + ∇ ⋅ ( ρu ) = Q (5-10)
∂t p br

ρ-  ∂u
+ ( u ⋅ ∇ ) ----- =
---- u
εp  ∂ t εp
(5-11)
1 T 2   –1 Q br
–∇ p + ∇ ⋅ ----
- --
- --------
-
μ ( ∇u + ( ∇u ) ) – μ ( ∇ ⋅ u )I  –  κ μ + 2  u + F
ε p  3   εp 

In these equations:

• μ (SI unit: kg/(m·s)) is the dynamic viscosity of the fluid

• u (SI unit: m/s) is the velocity vector
• ρ (SI unit: kg/m3) is the density of the fluid
• p (SI unit: Pa) is the pressure
• εp is the porosity
• κ (SI unit: m2) is the permeability tensor of the porous medium, and
• Qbr (SI unit: kg/(m3·s)) is a mass source or mass sink

Influence of gravity and other volume forces can be accounted for via the force term
F (SI unit: kg/(m2·s2)).

When the Neglect inertial term (Stokes-Brinkman) check box is selected, the term
(u · ∇)(u/εp) on the left-hand side of Equation 5-11 is disabled.

The mass source, Qbr, accounts for mass deposit and mass creation within the domains.
The mass exchange is assumed to occur at zero velocity.

The Forchheimer drag option, βF (SI unit: kg/m4), adds a viscous force proportional
to the square of the fluid velocity, FF = −βF|u|u, to the right-hand side of
Equation 5-11.

In case of a flow with variable density, Equation 5-10 and Equation 5-11 must be
solved together with the equation of state that relates the density to the temperature
and pressure (for instance the ideal gas law).

For incompressible flow, the density stays constant in any fluid particle, which can be
expressed as

∂ ( ε ρ ) + u ⋅ ∇ρ = 0
∂t p

286 | CHAPTER 5: FLUID FLOW INTERFACES

and the continuity equation (Equation 5-10) reduces to

ρ∇ ⋅ u = Q br

References for the Brinkman Equations Interface

1. D. Nield and A. Bejan, Convection in Porous Media, 3rd ed., Springer, 2006.

2. M. Le Bars and M.G. Worster, “Interfacial Conditions Between a Pure Fluid and a
Porous Medium: Implications for Binary Alloy Solidification,” J. of Fluid Mechanics,
vol. 550, pp. 149–173, 2006.

THEORY FOR THE BRINKMAN EQUATIONS INTERFACE | 287

 Theory for the Coupling of Fluid
Flow to Electrochemical Reactions
This section briefly discusses Momentum Sources and Sinks. Also see Theory for the
Coupling of Mass Transport to Electrochemical Reactions for how to calculate molar
and mass fluxes, sources and sinks.

Momentum Sources and Sinks

The flow velocity, u (SI unit: m/s), at a boundary is coupled to the total mass flux of
the species at the electrode surface in the following way

1
u ⋅ n = ---
ρ  ni ⋅ n (5-12)
i

where ρ (SI unit: kg/m3) is the density of the flowing media, n the surface normal and
ni is the mass flux of species i.

For flow interfaces solving for the velocity field, no-slip conditions are applied at the
electrode surface, resulting in

1 
u = –  ---
ρ  Mi Ni n (5-13)
i

where Mi (SI unit: kg/mol) is the species mass and Ni (SI unit: mol/(m2·s)) the molar
flux calculated by Faraday’s law.

For a porous electrode the sum of all mass fluxes are added to the conservation
equation according to:

∂ρ
------ + ∇ ⋅ ( ρu ) =
∂t  Ri, mass (5-14)
i

Note that because the mass is usually not conserved within the species transporting
phase (the right-hand side above being nonzero), the velocity field is not divergence
free.

288 | CHAPTER 5: FLUID FLOW INTERFACES

 6

Heat Transfer Interfaces

As with all other physical descriptions simulated by COMSOL Multiphysics, any

description of heat transfer can be directly coupled to any other physical process.
This is particularly relevant for systems based on chemical reactions and mass
transfer along with fluid flow. These physics interfaces are found under the Heat
Transfer branch ( ).

The basic functionality for simulating heat transfer in homogeneous media is

described in The Heat Transfer Interfaces in the COMSOL Multiphysics Reference
Manual.

The Electrochemistry Module also provides extra functionality for simulating heat
transfer in porous media. The documentation of all features in The Heat Transfer
in Porous Media Interface is found in the Heat Transfer Module User’s Guide,
which is supplied with the Electrochemistry Module irrespective of whether a
separate Heat Transfer Module license is purchased.

In this chapter:

• Coupling of Heat Transfer to Electrochemical Reactions

289
 Coupling of Heat Transfer to
Electrochemical Reactions
Irreversible voltage losses in an electrochemical cell can occur due to the following
phenomena:

• Charge transport in the electrolyte (Joule heating)

• Charge transport in the solid conductor materials (Joule heating)
• Activation overpotentials in the electrode reactions

In addition, reversible heat sources and sinks can appear due to the entropy changes in
the electrode reactions. How these heat sources are defined are described at the end of
this chapter.

Most Electrochemistry interfaces define and announce heat source variables that for
instance can be used by the General Source and the Boundary Heat source nodes in
the Heat Transfer interfaces.

An alternative way to couple an electrochemical interface to a heat transfer interface is

by the use of the Multiphysics nodes that become available in the model builder tree if
there is both a Heat Transfer interface and an Electrochemistry interface available in
the same component.

The Electrochemical Heating multiphysics node defines a domain heat source in the
heat transfer interface, based on the sum of irreversible (Joule heating and activation
losses) and reversible heat in the electrochemistry interface.

The Temperature Coupling node can be used to set the temperature in the
electrochemistry interface to equal the temperature dependent variable in the heat
transfer interface.

You can also use the heat source variables defined by the electrochemistry interfaces
when setting up manual heat couplings between different components in a model. For
instance if you are using a 1D electrochemical cell model to calculate an average heat
source in a 3D heat transfer model. The names of the heat source variables are xxx.Qh

290 | CHAPTER 6: HEAT TRANSFER INTERFACES

(domain, Joule heating and porous electrode reactions) and xxx.Qbfc (boundary,
electrode surface reactions), where xxx is the electrochemistry interface identifier.

• Electrochemistry Interfaces
• Multiphysics Coupling Nodes

Joule Heating Due to Charge Transport

The charge transport in the solid conductor material and electrolyte create joule
heating source terms according to

Q JH = – ( i s ⋅ ∇φ s + i l ⋅ ∇φ l ) (6-1)

Heating Due to Electrochemical Reactions

For an electrochemical reaction process one can write the total heat balance as:

• Heat generated = Total reaction enthalpy – Electrical energy leaving the system
Using Faraday’s law for an electrode reaction, m, at the interface between the electron
and ion conducting phase this corresponds to

ΔH m ΔG m
Q m =  ------------- –  ------------- – η m, tot  i m (6-2)
 nm F  nm F 

where ΔHm is the enthalpy change of the reaction, and ΔGm is the Gibbs free energy
of the reaction, ΔGm, defined as

ΔG m = ΔH m – TΔS m

where ΔSm is the net entropy change. The equilibrium potential is related to ΔGm in
the following way:

ΔG m
E eq, m = – -------------
nm F

In Equation 6-2 we have used the total overpotential, ηm,tot,(including potential

effects from film resistances and similar), defined as

η m, tot = φ s – φ l – E eq, m

By the relation

COUPLING OF HEAT TRANSFER TO ELECTROCHEMICAL REACTIONS | 291

 ∂E eq, m ΔS m
------------------
- = -----------
-
∂T nm F

the local heat source due to the electrochemical conversion process becomes

∂E eq, m
Q m =  η m, tot + T ------------------- i m
 ∂T 

where the overpotential expression represents the irreversible activation losses, and the
last term is the reversible heat change due to the net change of entropy in the
conversion process.

The total heat source due to the electrochemical reactions, QEC, for an electrode
surface is the sum of all individual heat sources of the electrode reactions according to

Q EC =  Qm
m

For a porous electrode joule heating and electrochemical sources are summed up for a
total heat source in the domain according to

Q TOT, p =  av, m Qm + QJH

m

TOTAL OVERPOTENTIAL CALCULATION FOR CONCENTRATION

DEPENDENT KINETICS
When using the Concentration Dependent kinetics option, in the Porous Electrode
Reaction and Electrode Reaction nodes, the equilibrium potential is typically a
constant referring to a reference state, and the concentration dependence of the
kinetics is accounted for only in the pre-exponential terms according to

α a, m Fη m – α c, m Fη m
i loc, m = i 0, m  C R, m exp  ------------------------- – C O, m exp  ---------------------------- 
  RT   RT 

where

η m = φ s – φ l – E eq, m

A result of this is that, when the pre-exponential factors CO,m and CR,m differ due to
concentration gradients, we at zero activation overpotential may have a net
charge-transfer current density flowing over the electrode-electrolyte interface. This

292 | CHAPTER 6: HEAT TRANSFER INTERFACES

local current density obviously should give rise to a heat source. The solution is to add
a concentration overpotential term to the total overpotential when calculating the heat
sources.

When using the Concentration Dependent kinetics option, the overpotential, used in
the irreversible heat term above, is calculated as follows:

η m, tot = φ s – φ l – E eq, m + η m, conc

where

RT C O, m
η m, conc = ------------ ln --------------
n m F C R, m

If the number of electrons is not available,

nm = α · + α c, m
a, m

is assumed.

The above concentration overpotential addition to the total overpotential is also used
for the Electroanalytical Butler-Volmer kinetics in the Electroanalysis interface.

COUPLING OF HEAT TRANSFER TO ELECTROCHEMICAL REACTIONS | 293

294 | CHAPTER 6: HEAT TRANSFER INTERFACES
 7

Multiphysics Coupling Nodes

The Electrochemistry Module has multiphysics couplings available under certain

conditions.

When a predefined multiphysics interface is added from the Model Wizard or Add
Physics windows, it adds the constituent interfaces and the Multiphysics Couplings
node, which automatically includes one or more multiphysics couplings.

If the constituent physics interfaces are added one at a time, then it adds an empty
Multiphysics Couplings node. When you right-click this node, you can choose from
the available multiphysics couplings.

The Multiphysics Branch in the COMSOL Multiphysics Reference

Manual.

In this chapter, the following multiphysics couplings nodes are described:

• Electrochemical Heating • Potential Coupling

• Flow Coupling • Space Charge Density Coupling
• Temperature Coupling

295
 Electrochemical Heating
Use the Electrochemical Heating multiphysics coupling ( ) to define domain and
boundary heat sources in a heat transfer interface, based on the sum of irreversible
(Joule heating and activation losses) and reversible heat in an electrochemistry
interface. The node also defines the temperature in the electrochemistry interface to
be equal to that of the heat transfer interface.

The settings of this node are similar to the Electromagnetic Heating node, described
in the COMSOL Multiphysics Reference Manual.

Coupling of Heat Transfer to Electrochemical Reactions

Flow Coupling
The Flow Coupling multiphysics coupling ( ) defines u and p variables in order to set
the model inputs in a physics interface that defines convective transport. In addition,
it provides all the fluids quantities that may be needed by the interface (for example,
viscosity and turbulence parameters).

SETTINGS
The Label is the default multiphysics coupling feature name.

The Name is used primarily as a scope prefix for variables defined by the coupling node.
Refer to such variables in expressions using the pattern <name>.<variable_name>. In
order to distinguish between variables belonging to different coupling nodes or physics
interfaces, the name string must be unique. Only letters, numbers, and underscores (_)
are permitted in the Name field. The first character must be a letter.

The default Name (for the first multiphysics coupling feature in the model) is fc1.

FLOW COUPLING
This section defines the physics involved in the multiphysics coupling. By default, the
applicable physics interface is selected in the Source list to apply the Destination to its
physics interface to establish the coupling.

You can also select None from either list to uncouple the node from a physics interface.
If the physics interface is removed from the Model Builder — for example, Heat Transfer

296 | CHAPTER 7: MULTIPHYSICS COUPLING NODES

in Solids is deleted — then the Destination list defaults to None as there is nothing to
couple to.

If a physics interface is deleted and then added to the model again, and in
order to reestablish the coupling, you need to choose the physics interface
again from the lists. This is applicable to all multiphysics coupling nodes
that would normally default to the once present physics interface. See
Multiphysics Modeling Approaches in the COMSOL Multiphysics
Reference Manual.

Potential Coupling
The Potential Coupling multiphysics coupling ( ) applies the electrolyte potential
variable from the source interface into the model inputs of the destination interface.
The potential variable is typically used to compute the migration flux in the destination
interface.

COUPLED INTERFACES
Specify the physics interface that provides the potential (Electrostatics, for instance) in
the Source list and the Chemical Species Transport interface in the Destination list.

Space Charge Density Coupling

The Space Charge Density Coupling multiphysics coupling ( ) computes the local
space charge, based on the local concentrations and species charges in a Chemical
Species Transport interface, and adds it to Poisson’s equation in an Electrostatics
interface.

COUPLED INTERFACES
Specify the Chemical Species Transport interface in the Source list and the
Electrostatics interface in the Destination list.

Temperature Coupling
Use the Temperature Coupling multiphysics coupling ( ) to add the temperature as
the default model input for a standalone physics interface.

The Temperature Coupling feature is generic and specifies a Heat Transfer interface as
Source and a second interface as Destination. When Temperature Coupling feature is

| 297
 used, the temperature from the Source is used to evaluate material properties in any
feature from the Destination interface. The coupling can be added wherever the Heat
Transfer interface is active.

The Source interface can be any interface defining a temperature, which includes all
versions of heat transfer and multiphysics, except the pure radiation interfaces.

The Destination interface can be any interface providing multiphysics feature in the
Multiphysics Couplings node — for example, Electric Current or Solid Mechanics.

See Coupled Interfaces in the COMSOL Multiphysics Reference Manual for more
details about this multiphysics coupling.

298 | CHAPTER 7: MULTIPHYSICS COUPLING NODES

 8

Glossary

This Glossary of Terms contains application-specific terms used in the

Electrochemistry Module software and documentation. For finite element
modeling terms, mathematical terms, and geometry and CAD terms, see the
glossary in the COMSOL Multiphysics Reference Manual. For references to more
information about a term, see the index.

299
 Glossary of Terms
anode An electrode where oxidation occurs. Anodic charge transfer current densities
and overpotentials are positive by definition.

cathode An electrode where reduction occurs. Cathodic charge transfer current

densities and overpotentials are negative by definition.

cell voltage The difference in potential over an electrochemical cell.

charge transfer reaction A reaction during which charge is transferred from an

electron conducting phase (electrode) to an ion conducting phase (electrolyte).

charge transfer current density The current density at an electrolyte-electrode

interface associated with a charge transfer reaction.

concentrated electrolyte An electrolyte where the concentration of charged species is

so high that the interactions between the ions needs to be considered. See also diluted
electrolyte.

current collector A part of an electrochemical device with high electric conductivity

for conducting current out of the cell. See also current feeder.

current feeder A part of an electrochemical device with high electric conductivity for
conducting current into the cell. See also current collector.

diluted electrolyte An electrolyte where the charged species are diluted in a solvent so
that the interaction between the ions can be neglected. See also concentrated
electrolyte.

electric potential The potential in the electrode (electron conducting) phase, denoted
φs (phis).

electrode An electron conductor.

electrode reaction See charge transfer reaction.

electrokinetic flow Transport of fluid or charged particles within a fluid by means of

electric fields.

300 | CHAPTER 8: GLOSSARY

electrolyte An ion conductor.

electrolyte potential The potential in the electrolyte (ionic) phase, denoted φl (phil).

electroneutrality A situation where the net charge of any small control volume of a
domain is zero. Electroneutrality can usually be assumed for electrolytes, with an
exception for the very proximity of the electrolyte-electrode interface, which is due to
the charge separation within the electrochemical double layer.

equilibrium potential The potential difference between the electrode and electrolyte
at which the net current density of an electrode reaction is zero.

Faraday’s Law A mathematical expression relating the flux of a species over an

electrode-electrolyte interphase to be proportional to the charge transfer current
density.

gas diffusion electrode (GDE) A porous electrode that also includes gas pores in the
porous matrix.

GDE See gas diffusion electrode (GDE).

Gibbs free energy A thermodynamic potential that depends on the enthalpy and
entropy of the reacting species.

intrinsic volume averages The physical properties of the fluid, such as density,
viscosity, and pressure.

intercalation The process of ions reacting on the surface of a host particle to form a
solid, intercalated, species within the host. The intercalated species can then be
transported further into the particle by diffusion processes.

migration The transport of charged species in an electrolyte due to the electric force
imposed by the electric field.

morphology correction parameter A correction parameter that is used to account for

morphology effects of a porous structure.

Nernst-Planck equation A commonly used equation for describing the transport of

charged species in a diluted electrolyte. The equation includes transport due to
diffusion, migration and convection. The Nernst-Planck equation can be modeled in

GLOSSARY OF TERMS | 301

 COMSOL Multiphysics using the Transport of Diluted Species interface. The
Nernst-Planck equation is often combined with an electroneutrality condition, which
can be modeled in COMSOL Multiphysics using the Tertiary Current Distribution,
Nernst-Planck interface.

Nernst-Planck-Poisson equation In certain situations, for instance when striving to

resolve the electrochemical double layer at an electrode, and electrokinetic flow cannot
be assumed, the Nernst-Planck equation is combined with the Poisson’s equation for
describing the charge density.

overpotential A deviation from the equilibrium potential.

oxidation A charge transfer reaction where electrons are produced.

perfectly mixed electrolyte. An electrolyte where no concentration gradients are

present, for instance due to stirring. See also secondary current distribution.

primary current distribution The current distribution that is established when

overpotentials can be neglected—that is, when the current distribution is governed by
the electrolyte and electrode conductivities only. See also secondary current
distribution and tertiary current distribution.

Poisson’s equation An equation for relating the electric field to the space charge
density. Can be modeled in COMSOL using the Electrostatics interface.

pore electrolyte An electrolyte in the pores of a porous matrix. See porous electrode.

porous electrode A porous matrix containing both electron conducting and ion
conducting media.

potentiostat A device that monitors and controls the potential of an electrode versus
a reference electrode.

reduction A charge transfer reaction where electrons are consumed.

reference electrode An electrode used for reference when defining the potentials of
the electrodes in a cell. A good reference electrode is stable and does not vary in
potential. Typically no net reactions occur at a reference electrode surface, and the net
current density is zero.

302 | CHAPTER 8: GLOSSARY

resistive film A film with ohmic resistivity, typically formed as a result of electrode
reactions.

secondary current distribution The current distribution that is established when

concentration overpotentials can be neglected—that is, when the current distribution
is governed by the activation overpotentials and the electrolyte conductivity. See also
tertiary current distribution and primary current distribution. Note that COMSOL
models using the Secondary Current Distribution interface can in fact be modeling a
tertiary current distribution because mass transport activation losses can be present in
the electrode reaction current density expressions.

solid-electrolyte interphase (SEI) A resistive and passivating layer formed on the

graphite electrode particles in the negative electrode of a lithium-ion battery.

stoichiometric coefficients The number of species reacting in a reaction formula. In a

redox reaction the oxidized species have negative sign and the reduced species have
positive sign by convention.

superficial volume averages The flow velocities, which correspond to a unit volume of
the medium including both pores and matrix. These are sometimes called
Darcy velocities, defined as volume flow rates per unit cross section of the medium.

supporting electrolyte An electrolyte with an excess of charge carriers so that the

conductivity can be assumed not to be affected by the currents flowing in the cell.

surface molar flux The tangential flux in the surface dimension as governed by
diffusion according to Fick’s law.

tertiary current distribution The current distribution that is established when

concentration overpotentials cannot be neglected — that is, when the current
distribution is governed by the activation and concentration overpotentials, as well as
the electrolyte conductivity. The electrolyte conductivity can also be nonconstant due
to the currents flowing in the cell. See also secondary current distribution and primary
current distribution.

GLOSSARY OF TERMS | 303

304 | CHAPTER 8: GLOSSARY
I n d e x
A absolute pressure 281 secondary current distribution 111
activation overpotential 111, 116, 135 Butler–Volmer equation
adsorption 173 electroanalysis 137
amperometric sensing 132
C cathodes 30
analyte 132
cathodic charge transfer coefficient 111
anodes 30
cathodic Tafel equation 117
anodic Tafel equation 117
CFL number
anodic transfer coefficient 111
settings 277
Application Libraries window 21
charge transfer reaction 110
application library examples
charge transfer reactions 81, 106
convection and diffusion 157
checklist, for modeling 49
electroanalysis interface 100
chemical equilibrium 187
electrode surface feature 106
chronoamperometry 132
migration in electric field 157
common settings 18
secondary current distribution 61
concentration (node)
transport of diluted species 152
transport of diluted species 161
Arrhenius parameters 189
continuity equation, Darcy’s law 282
B boundary current source (node) 97 convection 231
boundary electrolyte potential 86, 210 convective terms, diluted species 223
boundary nodes coulometry 132
Brinkman equations 277 current (node) 210
Darcy’s law interface 259 current density (node) 210
electroanalysis 101 current source (node) 96
electrochemistry interfaces 75 cyclic voltammetry 132
electrode, shell 94
D Darcy velocity 264, 282
free and porous media flow 269
Darcy’s law interface 258
surface reactions 215
theory 282
transport of diluted species 153, 206
Debye length 34
Brinkman equations 285
documentation 20
Brinkman equations interface 275
domain nodes
theory 285
Brinkman equations 277
Butler-Volmer and Tafel expressions
Darcy’s law 259
tertiary current distribution 66
electroanalysis 101
Butler-Volmer equation 39
electrochemistry interfaces 75
electrode kinetics 116
electrophoretic transport interface
porous electrodes 120

INDEX| 305
 206 electrode symmetry axis current source
free and porous media flow 269 (node) 64
transport of diluted species 153 electrode, shell interface 93
double layer capacitance (node) 85 theory 130
electrode-electrolyte boundary interface
E edge electrode (node) 63
(node)
edge nodes
current distribution 87
Darcy’s law interface 259
electrode-electrolyte interface coupling
electrochemistry interfaces 75
(node)
electrode, shell 94
free and porous media flow 263, 273
surface reactions 215
transport of diluted species 170
electric insulation (node)
electrode-electrolyte interfaces 30
electrode, shell 97
electrodes 29
electric potential (node)
electrolysis 29
electrode, shell 98
electrolyte 110
electric reference potential (node) 91
electrolyte (node)
electroanalysis interface 99
primary and secondary current distri-
theory 132
bution 61
electroanalysis, definition 132
tertiary current distribution 70
electrochemical cells 30
electrolyte current (node) 86
electrochemical impedance spectrosco-
electrolyte current density (node) 87
py (EIS) 132
electrolyte current source (node) 77
electrochemical sensing 132
electrolyte line current source (node) 64
electrode 110
electrolyte points current source (node)
electrode (node)
65
electrochemistry 76
electrolyte potential 113
electrode, shell 95
electrolyte potential (node) 86
electrode current (node) 89
electrolyte symmetry axis current
electrode current density (node) 88
source (node) 65
electrode current source (node) 77
electrolyte-electrode domain interface
electrode line current source (node) 64
(node) 85
electrode points current source (node)
electrolytes 29
65
electromagnetic heat source (multiphys-
electrode potential (node) 90
ics coupling) 296
electrode power (node) 89
electroneutrality 34
electrode reaction (node)
electrophoretic transport nterface 200
electroanalysis 106
electrophoretictransport 200
electrochemistry 81
emailing COMSOL 22
electrode surface (node) 79, 104

306 | I N D E X
 equilibrium potential 111 Hygroscopic Swelling 182
Equilibrium Reaction
I inflow (node) 160, 212
theory for 221
initial values (node)
equilibrium reaction (node) 167
Brinkman equations 280
equilibrium reaction group (node) 194
Darcy’s law 262
external short circuit (node) 90
electroanalysis 103
F faradaic current 43 electrode, shell 96
Faraday’s constant 111 free and porous media flow 273
Faraday’s law 227 primary and secondary current distri-
Faraday’s laws of electrolysis 136 bution 61
Fick diffusion laws 134 surface reactions 217
flow coupling (multiphysics coupling) 296 tertiary current distribution 72
fluid and matrix properties (node) transport of diluted species 158
Brinkman equations 278 inlet (node) 264
Darcy’s law 261 insulation (node) 79, 210
fluid flow internet resources 19
Brinkman equations theory 285 intrinsic volume averages 285
Darcy’s law theory 282 irreversible reaction 187
flux (node) 212
K knowledge base, COMSOL 23
transport of diluted species 161, 212
L Langmuir constant 236
flux discontinuity (node) 162
leaking wall, wall boundary condition 274
Darcy’s law 265
line mass source (node)
transport of diluted species 162
species transport 164
Forchheimer drag (node)
line source
Brinkman equations 279
species transport 225
free and porous media flow 272
liquid reacting fluids 185, 192
free and porous matrix properties
local
(node) 271
CFL number 277
free and porous media flow interface 268
theory 284 M mass based concentrations (node) 158
Freundlich exponent 236 mass flux (node) 264
mass source (node)
G galvanic cells 29
Brinkman equations 279
gas reacting fluids 185, 192
Darcy’s law 262
Gibbs free energy 191
modeling checklist 49
ground (node) 97
monolayer adsorption 250
H harmonic perturbation (node) 90
MPH-files 21
heterogeneous rate constant 137
multiphysics couplings

INDEX| 307
 electromagnetic heat source (node) transport of diluted species 153
296 partially saturated porous media (node)
flow coupling (node) 296 174
temperature coupling (node) 297 periodic condition (node) 62
transport of diluted species 164
N Nernst equation 137
permeability models 262
Nernst-Einstein relation 103, 156, 172,
physics interfaces, common settings 18
176, 226
point mass source (node)
Nernst-Planck equations 33, 108
species transport 165
nernst-planck-poission equations inter-
point nodes
face 198
Brinkman equations 277
Nernst-Planck-Poisson equations 34
Darcy’s law interface 259
no flow (node) 265
electrochemistry interfaces 75
no flux (node) 160
electrode, shell 94
no slip, wall boundary condition 274
free and porous media flow 269
nodes, common settings 18
surface reactions 215
non-conservative formulations 223
point source
normal current density (node) 97
species transport 224
O Ohm’s law 58, 109, 228
porous electrode (node) 62, 70
ohmic drop 133
porous electrode coupling (node) 169
open boundary (node)
free and porous media flow 262, 272
transport of diluted species 166
porous electrode reaction (node) 78
outflow (node)
porous electrodes 61, 110
electrophoretic transport 213
porous matrix double layer capacitance
transport of diluted species 161
(node) 78
outlet (node) 266
porous media and subsurface flow
overpotential 38, 111
Brinkman equations interface 275
P packed bed reactors 237 Darcy’s law interface 258
pair nodes free and porous media flow interface
Brinkman equations 277 268
Darcy’s law interface 259 theory, Brinkman equations 285
electroanalysis 101 theory, Darcy’s law 282
electrochemistry interfaces 75 theory, free and porous media flow
electrode, shell 94 284
electrophoretic transport interface porous media transport properties
206 (node) 171
free and porous media flow 269 potential (node) 210
surface reactions 215 potentiometry 132

308 | I N D E X
 potentiostat 140 stoichiometric coefficients 191
pressure (node) 263 stratified porous media 235
primary current distribution 31 study types
primary current distribution interface 58 physics interface availability 18
theory 108 superficial volume average, porous me-
pseudo time stepping dia 285
settings 277 superficial volume averages, porous me-
dia 231
R reacting fluids, gases and liquids 185, 192
supporting electrolyte 133
Reacting Volume 159
Supporting Electrolytes 227
reaction (node) 187
surface concentration (node) 218
reaction coefficients (node) 170
surface equilibrium reaction (node) 168
reaction thermodynamics (node) 196
surface properties (node) 216
Reactions
surface reactions interface 214
in porous catalyst pellets 180
theory 249
reactions (node)
symmetry (node)
surface reactions 217
Darcy’s law 265
tertiary current distribution 71
electrochemistry 79
transport of diluted species 158
transport of diluted species 162
reactive pellet bed 237
reactive pellet bed (node) 177 T Tafel equation 117
reference electrode (node) 91 Tafel law 39
resistive film 116 technical support, COMSOL 22
retardation factor 236 temperature coupling (multiphysics cou-
reversible reaction 187 pling) 297
reversible reaction group (node) 193 tertiary current distribution 31
tertiary current distribution interface
S secondary current distribution 31
theory 108
secondary current distribution interface
tertiary current distribution,
58
Nernst-Planck interface 66
theory 108
theory
separator (node)
Brinkman equations 285
current distribution 71
Darcy’s law 282
slip, wall boundary condition 274
electroanalysis interface 132
species (node) 191
electrode, shell interface 130
species activity (node) 196
free and porous media flow 284
species group (node) 196
primary current distribution interface
species source (node) 211
108
species thermodynamics (node) 196
secondary current distribution inter-
standard settings 18

INDEX| 309
 face 108
surface reactions 249
tertiary current distribution interface
108
transport of diluted species in porous
media interface 219
transport of diluted species interface
219
thickness
fracture 183
out-of-plane 267
thin diffusion barrier (node) 166
Thin Impermeable Barrier 166
tortuosity factors 233
transport mechanisms 102
transport of diluted species in porous
media interface 152
theory 219
transport of diluted species interface 148
theory 219
turbulent mixing (node)
transport of diluted species 157

V voltammetry, cyclic 132

volume averages 285
volume force (node) 280
free and porous media flow 272

W wall (node)
free and porous media flow 274
websites, COMSOL 22

310 | I N D E X