Electrodeposition Module

User’s Guide
Electrodeposition Module User’s Guide
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Part number: CM022501

C o n t e n t s

Chapter 1: Introduction

About the Electrodeposition Module 18

What Can the Electrodeposition Module Do? . . . . . . . . . . . . 18
The Electrodeposition Module Physics Interface Guide . . . . . . . . 19
Common Physics Interface and Feature Settings and Nodes . . . . . . 22
Where Do I Access the Documentation and Application Libraries? . . . . 23

Overview of the User’s Guide 27

Chapter 2: Modeling with Electrochemistry

Introduction to Electrochemistry Modeling 30

What Is Electrochemistry? . . . . . . . . . . . . . . . . . . . 30
Electrochemical Applications . . . . . . . . . . . . . . . . . . 31
Fundamentals of Electrochemistry Modeling . . . . . . . . . . . . 31
Current Distribution Cases and Choosing the Right Interface to
Model an Electrochemical Cell . . . . . . . . . . . . . . . . 33
Understanding the Different Approximations for Conservation of
Charge in Electrolytes . . . . . . . . . . . . . . . . . . . 34
Modeling Electrochemical Reactions . . . . . . . . . . . . . . . 38
Double Layer Capacitance . . . . . . . . . . . . . . . . . . . 45
Porous Electrodes . . . . . . . . . . . . . . . . . . . . . . 46
Boundary Conditions for Running and Controlling Electrochemical
Cells . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Modeling Cyclic Voltammetry . . . . . . . . . . . . . . . . . . 48
Common Simplifications When Modeling Electrochemical Cells . . . . . 48
Before You Start Building Your Model . . . . . . . . . . . . . . . 50
Meshing Advice . . . . . . . . . . . . . . . . . . . . . . . 52
Solving Electrochemical Models . . . . . . . . . . . . . . . . . 52
Postprocessing Your Solution . . . . . . . . . . . . . . . . . . 57

CONTENTS |3
 Chapter 3: Electrochemistry Interfaces

The Primary and Secondary Current Distribution Interfaces 60

The Primary Current Distribution and Secondary Current Distribution
Interfaces . . . . . . . . . . . . . . . . . . . . . . . . 60
Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . . 63
Initial Values . . . . . . . . . . . . . . . . . . . . . . . . 64
Porous Electrode. . . . . . . . . . . . . . . . . . . . . . . 64
Periodic Condition . . . . . . . . . . . . . . . . . . . . . . 66
Thin Electrolyte Layer . . . . . . . . . . . . . . . . . . . . . 66
Edge Electrode. . . . . . . . . . . . . . . . . . . . . . . . 67
Electrode Line Current Source . . . . . . . . . . . . . . . . . 68
Electrolyte Line Current Source . . . . . . . . . . . . . . . . . 69
Electrode Symmetry Axis Current Source . . . . . . . . . . . . . 69
Electrolyte Symmetry Axis Current Source . . . . . . . . . . . . . 69
Electrode Point Current Source . . . . . . . . . . . . . . . . . 70
Electrolyte Point Current Source. . . . . . . . . . . . . . . . . 70
Electrode Current . . . . . . . . . . . . . . . . . . . . . . 70

The Tertiary Current Distribution, Nernst-Planck Interface 71

The Tertiary Current Distribution, Nernst–Planck Interface . . . . . . 71
Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . . 75
Porous Electrode. . . . . . . . . . . . . . . . . . . . . . . 76
Separator. . . . . . . . . . . . . . . . . . . . . . . . . . 77
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . 78
Initial Values . . . . . . . . . . . . . . . . . . . . . . . . 78
Ion Exchange Membrane . . . . . . . . . . . . . . . . . . . . 79
Ion Exchange Membrane Boundary . . . . . . . . . . . . . . . . 79
Thin Electrolyte Layer . . . . . . . . . . . . . . . . . . . . . 80

The Current Distribution, Boundary Elements Interface 81

The Current Distribution, Boundary Elements Interface . . . . . . . . 81
Edge Features in 3D for the Current Distribution, Boundary
Elements Interface. . . . . . . . . . . . . . . . . . . . . . 83

Shared Physics Features in the Current Distribution Interfaces

4 | CONTENTS
 85
Domain, Boundary, Pair, Edge, and Point Nodes for the
Electrochemistry Interfaces . . . . . . . . . . . . . . . . . 85
Electrode. . . . . . . . . . . . . . . . . . . . . . . . . . 87
Highly Conductive Porous Electrode . . . . . . . . . . . . . . . 87
Electrode Current Source . . . . . . . . . . . . . . . . . . . 87
Electrolyte Current Source . . . . . . . . . . . . . . . . . . . 88
Porous Electrode Reaction . . . . . . . . . . . . . . . . . . . 88
Porous Matrix Double Layer Capacitance . . . . . . . . . . . . . 89
Insulation . . . . . . . . . . . . . . . . . . . . . . . . . . 89
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . . 89
Electrode Surface. . . . . . . . . . . . . . . . . . . . . . . 90
Electrode Reaction . . . . . . . . . . . . . . . . . . . . . . 94
Double Layer Capacitance . . . . . . . . . . . . . . . . . . 100
Perforated Electrode Surface . . . . . . . . . . . . . . . . . 100
Internal Electrode Surface . . . . . . . . . . . . . . . . . . 100
Thin Electrode Surface. . . . . . . . . . . . . . . . . . . . 101
Electrolyte Potential . . . . . . . . . . . . . . . . . . . . 102
Electrolyte Current . . . . . . . . . . . . . . . . . . . . . 102
Electrolyte Current Density. . . . . . . . . . . . . . . . . . 103
Thin Electrode Layer . . . . . . . . . . . . . . . . . . . . 103
Electrode-Electrolyte Boundary Interface. . . . . . . . . . . . . 104
Electric Ground . . . . . . . . . . . . . . . . . . . . . . 105
Electric Potential . . . . . . . . . . . . . . . . . . . . . . 105
Electrode Current Density . . . . . . . . . . . . . . . . . . 105
Electrode Current . . . . . . . . . . . . . . . . . . . . . 106
Electrode Power . . . . . . . . . . . . . . . . . . . . . . 106
Harmonic Perturbation . . . . . . . . . . . . . . . . . . . 107
Electrode Potential . . . . . . . . . . . . . . . . . . . . . 107
External Short . . . . . . . . . . . . . . . . . . . . . . . 107
Initial Values for Adsorbing-Desorbing Species. . . . . . . . . . . 108
Initial Values for Dissolving-Depositing Species . . . . . . . . . . 108
Non-Faradaic Reactions . . . . . . . . . . . . . . . . . . . 108
Reference Electrode . . . . . . . . . . . . . . . . . . . . 109
Electric Reference Potential . . . . . . . . . . . . . . . . . . 109
Circuit Terminal . . . . . . . . . . . . . . . . . . . . . . 109

CONTENTS |5
 The Electrode, Shell Interface 110
Boundary, Edge, Point, and Pair Nodes for the Electrode, Shell
Interface. . . . . . . . . . . . . . . . . . . . . . . . 111
Electrode . . . . . . . . . . . . . . . . . . . . . . . . . 112
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 113
Depositing Electrode . . . . . . . . . . . . . . . . . . . . 113
External Current Density . . . . . . . . . . . . . . . . . . 114
Current Source . . . . . . . . . . . . . . . . . . . . . . 114
Normal Current Density . . . . . . . . . . . . . . . . . . . 114
Electric Insulation . . . . . . . . . . . . . . . . . . . . . 115
Boundary Current Source . . . . . . . . . . . . . . . . . . 115
Ground . . . . . . . . . . . . . . . . . . . . . . . . . 115
Electric Potential . . . . . . . . . . . . . . . . . . . . . . 115

The Electroanalysis Model Wizard Entry 117

Theory for the Current Distribution Interfaces 118

The Nernst-Planck Equations . . . . . . . . . . . . . . . . . 118
Domain Equations for Primary and Secondary Current Distributions . . 119
Electrochemical Reactions and the Difference Between a Primary and
a Secondary Current Distribution . . . . . . . . . . . . . . 120
Domain Equations for Tertiary Current Distributions Using the
Nernst-Planck Equations and Electroneutrality . . . . . . . . . 123
Mass Fluxes and Sources Due to Electrochemical Reactions . . . . . 124
Deposition-Dissolution Rates, Growth Velocities, and Thicknesses on
an Electrode Surface . . . . . . . . . . . . . . . . . . . 125
Stoichiometric Coefficients for Double Layer Capacitive Charging . . . 126
Film Resistance . . . . . . . . . . . . . . . . . . . . . . 126
Equilibrium Potentials and the Nernst Equation . . . . . . . . . . 127
Electrode Kinetics Expressions . . . . . . . . . . . . . . . . 128
Theory for Specific Current Distribution Feature Nodes . . . . . . . 133
References . . . . . . . . . . . . . . . . . . . . . . . . 140

Theory for Electrochemical Heat Sources 142

Joule Heating Due to Charge Transport . . . . . . . . . . . . . 143
Heating Due to Electrochemical Reactions . . . . . . . . . . . . 143
Heating Due to Heat of Mixing . . . . . . . . . . . . . . . . 144

6 | CONTENTS
 Theory for the Electrode, Shell Interface 146
Governing Equations . . . . . . . . . . . . . . . . . . . . 146
Coupling to Other Physics Interfaces . . . . . . . . . . . . . . 146

Theory for Electroanalysis 148

Electroanalytical Methods . . . . . . . . . . . . . . . . . . 148
Supporting Electrolyte . . . . . . . . . . . . . . . . . . . . 148
Domain Equations for the Electroanalysis Case . . . . . . . . . . 149
Electrode Boundary Conditions in the Electroanalysis Model . . . . . 151
The Electroanalytical Butler-Volmer Equation . . . . . . . . . . . 153
Counter Electrodes and Overall Charge Balance . . . . . . . . . . 154

Electrode Potentials and Reference Electrodes 155

Reference Electrodes . . . . . . . . . . . . . . . . . . . . 155
Boundary Conditions Using Reference Electrode Potentials. . . . . . 156
Nodes for Handling Electrode Potentials and Reference Electrodes. . . 156

Chapter 4: Electrodeposition, Deformed Geometry

Interfaces

About the Electrodeposition, Deformed Geometry Interfaces 160

Modeling Deformation of an Electrode Surface . . . . . . . . . . 161
Tangential Velocities at the Intersection Between a Depositing and a
Nondepositing Boundary . . . . . . . . . . . . . . . . . 161

Chapter 5: Chemical Species Transport Interfaces

The Transport of Diluted Species Interface 166

The Transport of Diluted Species in Porous Media Interface . . . . . 170
Domain, Boundary, and Pair Nodes for the Transport of Diluted
Species Interface. . . . . . . . . . . . . . . . . . . . . 171
Transport Properties . . . . . . . . . . . . . . . . . . . . 174
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 176
Mass-Based Concentrations . . . . . . . . . . . . . . . . . . 176

CONTENTS |7
 Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 177
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 178
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 179
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 180
Concentration . . . . . . . . . . . . . . . . . . . . . . . 180
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 182
Flux Discontinuity . . . . . . . . . . . . . . . . . . . . . 182
Partition Condition . . . . . . . . . . . . . . . . . . . . . 182
Periodic Condition . . . . . . . . . . . . . . . . . . . . . 183
Line Mass Source . . . . . . . . . . . . . . . . . . . . . . 184
Point Mass Source . . . . . . . . . . . . . . . . . . . . . 185
Open Boundary . . . . . . . . . . . . . . . . . . . . . . 185
Thin Diffusion Barrier . . . . . . . . . . . . . . . . . . . . 186
Thin Impermeable Barrier . . . . . . . . . . . . . . . . . . 186
Equilibrium Reaction . . . . . . . . . . . . . . . . . . . . 186
Surface Reactions . . . . . . . . . . . . . . . . . . . . . 187
Surface Equilibrium Reaction . . . . . . . . . . . . . . . . . 188
Fast Irreversible Surface Reaction . . . . . . . . . . . . . . . 188
Porous Electrode Coupling . . . . . . . . . . . . . . . . . . 189
Reaction Coefficients . . . . . . . . . . . . . . . . . . . . 189
Electrode Surface Coupling . . . . . . . . . . . . . . . . . . 190
Porous Medium . . . . . . . . . . . . . . . . . . . . . . 190
Fluid . . . . . . . . . . . . . . . . . . . . . . . . . . 191
Porous Matrix . . . . . . . . . . . . . . . . . . . . . . . 192
Dispersion . . . . . . . . . . . . . . . . . . . . . . . . 193
Unsaturated Porous Medium . . . . . . . . . . . . . . . . . 194
Liquid . . . . . . . . . . . . . . . . . . . . . . . . . . 194
Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . 197
Volatilization . . . . . . . . . . . . . . . . . . . . . . . 199
Species Source. . . . . . . . . . . . . . . . . . . . . . . 200
Hygroscopic Swelling . . . . . . . . . . . . . . . . . . . . 200
Out-of-Plane Flux . . . . . . . . . . . . . . . . . . . . . 201
Fracture . . . . . . . . . . . . . . . . . . . . . . . . . 203

The Chemistry Interface 205

Feature Nodes Available for the Chemistry Interface . . . . . . . . 210

8 | CONTENTS
Reaction . . . . . . . . . . . . . . . . . . . . . . . . . 210
Species . . . . . . . . . . . . . . . . . . . . . . . . . 215
Electrode Reaction . . . . . . . . . . . . . . . . . . . . . 217
Electrode Reaction Group . . . . . . . . . . . . . . . . . . 220
Reversible Reaction Group . . . . . . . . . . . . . . . . . . 220
Equilibrium Reaction Group. . . . . . . . . . . . . . . . . . 222
Species Group . . . . . . . . . . . . . . . . . . . . . . . 223
Reaction Thermodynamics . . . . . . . . . . . . . . . . . . 223
Species Activity . . . . . . . . . . . . . . . . . . . . . . 223
Species Thermodynamics. . . . . . . . . . . . . . . . . . . 224

The Nernst–Planck-Poisson Equations Interface 225

The Electrophoretic Transport Interface 227

Common Settings for the Species Nodes in the Electrophoretic
Transport Interface . . . . . . . . . . . . . . . . . . . 230
Diffusion and Migration Settings . . . . . . . . . . . . . . . . 232
Domain, Boundary, and Pair Nodes for the Electrophoretic Transport
Interface. . . . . . . . . . . . . . . . . . . . . . . . 233
Solvent . . . . . . . . . . . . . . . . . . . . . . . . . 234
Porous Matrix Properties . . . . . . . . . . . . . . . . . . 234
Fully Dissociated Species . . . . . . . . . . . . . . . . . . . 234
Uncharged Species . . . . . . . . . . . . . . . . . . . . . 234
Weak Acid . . . . . . . . . . . . . . . . . . . . . . . . 235
Weak Base . . . . . . . . . . . . . . . . . . . . . . . . 235
Ampholyte . . . . . . . . . . . . . . . . . . . . . . . . 235
Protein . . . . . . . . . . . . . . . . . . . . . . . . . 236
Current Source . . . . . . . . . . . . . . . . . . . . . . 236
Initial Potential. . . . . . . . . . . . . . . . . . . . . . . 236
Current . . . . . . . . . . . . . . . . . . . . . . . . . 236
Current Density . . . . . . . . . . . . . . . . . . . . . . 236
Insulation . . . . . . . . . . . . . . . . . . . . . . . . . 237
Potential . . . . . . . . . . . . . . . . . . . . . . . . . 237
Species Source. . . . . . . . . . . . . . . . . . . . . . . 237
Initial Concentration . . . . . . . . . . . . . . . . . . . . 238
Concentration . . . . . . . . . . . . . . . . . . . . . . . 238
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 238
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 238

CONTENTS |9
 Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 239
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 239

The Surface Reactions Interface 240

Boundary, Edge, Point, and Pair Nodes for the Surface Reactions
Interface. . . . . . . . . . . . . . . . . . . . . . . . 241
Surface Properties . . . . . . . . . . . . . . . . . . . . . 242
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 243
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 243
Surface Concentration . . . . . . . . . . . . . . . . . . . . 244

Theory for the Transport of Diluted Species Interface 245

Mass Balance Equation . . . . . . . . . . . . . . . . . . . . 246
Equilibrium Reaction Theory . . . . . . . . . . . . . . . . . 247
Convective Term Formulation. . . . . . . . . . . . . . . . . 249
Solving a Diffusion Equation Only . . . . . . . . . . . . . . . 250
Mass Sources for Species Transport . . . . . . . . . . . . . . 250
Adding Transport Through Migration . . . . . . . . . . . . . . 252
Supporting Electrolytes . . . . . . . . . . . . . . . . . . . 253
Crosswind Diffusion . . . . . . . . . . . . . . . . . . . . 254
Danckwerts Inflow Boundary Condition . . . . . . . . . . . . . 255
Mass Balance Equation for Transport of Diluted Species in Porous
Media . . . . . . . . . . . . . . . . . . . . . . . . . 256
Convection in Porous Media . . . . . . . . . . . . . . . . . 257
Diffusion in Porous Media . . . . . . . . . . . . . . . . . . 259
Dispersion . . . . . . . . . . . . . . . . . . . . . . . . 260
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . 262
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 264
Mass Transport in Fractures . . . . . . . . . . . . . . . . . 265
References . . . . . . . . . . . . . . . . . . . . . . . . 266

Theory for the Electrophoretic Transport Interface 268

Theory for the Surface Reactions Interface 274

Governing Equations for the Surface Concentrations . . . . . . . . 274
Governing Equations for the Bulk Concentrations . . . . . . . . . 275
ODE Formulations for Surface Concentrations . . . . . . . . . . 277
Surface Reaction Equations on Deforming Geometries . . . . . . . 278

10 | C O N T E N T S
 Reference for the Surface Reactions Interface . . . . . . . . . . . 279

Theory for the Coupling of Mass Transport to

Electrochemical Reactions 280
Molar Sources and Sinks . . . . . . . . . . . . . . . . . . . 280
Mass Sources and Sinks . . . . . . . . . . . . . . . . . . . 281

Chapter 6: Fluid Flow Interfaces

The Laminar Flow and Creeping Flow Interfaces 284

The Creeping Flow Interface . . . . . . . . . . . . . . . . . 284
The Laminar Flow Interface . . . . . . . . . . . . . . . . . . 285
Fluid Properties . . . . . . . . . . . . . . . . . . . . . . 291
Volume Force . . . . . . . . . . . . . . . . . . . . . . . 293
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 293
Wall . . . . . . . . . . . . . . . . . . . . . . . . . . 294
Inlet . . . . . . . . . . . . . . . . . . . . . . . . . . . 296
Outlet . . . . . . . . . . . . . . . . . . . . . . . . . . 300
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 303
Open Boundary . . . . . . . . . . . . . . . . . . . . . . 303
Boundary Stress . . . . . . . . . . . . . . . . . . . . . . 304
Periodic Flow Condition . . . . . . . . . . . . . . . . . . . 305
Flow Continuity . . . . . . . . . . . . . . . . . . . . . . 306
Pressure Point Constraint . . . . . . . . . . . . . . . . . . 307
Point Mass Source . . . . . . . . . . . . . . . . . . . . . 307
Line Mass Source . . . . . . . . . . . . . . . . . . . . . . 308
Gravity . . . . . . . . . . . . . . . . . . . . . . . . . 309

The Darcy’s Law Interface 310

Domain, Boundary, Edge, Point, and Pair Nodes for the Darcy’s
Law Interface . . . . . . . . . . . . . . . . . . . . . . 312
Porous Medium . . . . . . . . . . . . . . . . . . . . . . 314
Fluid . . . . . . . . . . . . . . . . . . . . . . . . . . 316
Porous Matrix . . . . . . . . . . . . . . . . . . . . . . . 317
Mass Source . . . . . . . . . . . . . . . . . . . . . . . 319
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 320

CONTENTS | 11
 Unsaturated Porous Medium . . . . . . . . . . . . . . . . . 320
Gravity . . . . . . . . . . . . . . . . . . . . . . . . . 321
Cross Section . . . . . . . . . . . . . . . . . . . . . . . 322
Thickness. . . . . . . . . . . . . . . . . . . . . . . . . 322
Porous Electrode Coupling . . . . . . . . . . . . . . . . . . 323
Electrode Surface Coupling . . . . . . . . . . . . . . . . . . 323
Pressure . . . . . . . . . . . . . . . . . . . . . . . . . 324
Mass Flux. . . . . . . . . . . . . . . . . . . . . . . . . 324
Line Mass Source . . . . . . . . . . . . . . . . . . . . . . 325
Point Mass Source . . . . . . . . . . . . . . . . . . . . . 325
Inlet . . . . . . . . . . . . . . . . . . . . . . . . . . . 326
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 327
No Flow . . . . . . . . . . . . . . . . . . . . . . . . . 327
Flux Discontinuity . . . . . . . . . . . . . . . . . . . . . 327
Outlet . . . . . . . . . . . . . . . . . . . . . . . . . . 328
Precipitation . . . . . . . . . . . . . . . . . . . . . . . 329
Interior Wall . . . . . . . . . . . . . . . . . . . . . . . 329
Thin Barrier. . . . . . . . . . . . . . . . . . . . . . . . 329
Pressure Head . . . . . . . . . . . . . . . . . . . . . . . 330
Hydraulic Head . . . . . . . . . . . . . . . . . . . . . . 330
Atmosphere/Gauge . . . . . . . . . . . . . . . . . . . . . 330
Pervious Layer . . . . . . . . . . . . . . . . . . . . . . . 331
Well . . . . . . . . . . . . . . . . . . . . . . . . . . 332
Fracture Flow . . . . . . . . . . . . . . . . . . . . . . . 333

The Free and Porous Media Flow Interface 334

Domain, Boundary, Point, and Pair Nodes for the Free and Porous
Media Flow Interface . . . . . . . . . . . . . . . . . . . 336
Fluid Properties . . . . . . . . . . . . . . . . . . . . . . 337
Porous Medium . . . . . . . . . . . . . . . . . . . . . . 338
Fluid . . . . . . . . . . . . . . . . . . . . . . . . . . 338
Porous Matrix . . . . . . . . . . . . . . . . . . . . . . . 339
Mass Source . . . . . . . . . . . . . . . . . . . . . . . 340
Volume Force . . . . . . . . . . . . . . . . . . . . . . . 340
Porous Electrode Coupling . . . . . . . . . . . . . . . . . . 340
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 341
Gravity . . . . . . . . . . . . . . . . . . . . . . . . . 341
Electrode-Electrolyte Interface Coupling . . . . . . . . . . . . . 341

12 | C O N T E N T S
Wall . . . . . . . . . . . . . . . . . . . . . . . . . . 342

The Brinkman Equations Interface 344

Domain, Boundary, Point, and Pair Nodes for the Brinkman
Equations Interface . . . . . . . . . . . . . . . . . . . . 347
Porous Medium . . . . . . . . . . . . . . . . . . . . . . 348
Fluid . . . . . . . . . . . . . . . . . . . . . . . . . . 348
Porous Matrix . . . . . . . . . . . . . . . . . . . . . . . 349
Mass Source . . . . . . . . . . . . . . . . . . . . . . . 350
Volume Force . . . . . . . . . . . . . . . . . . . . . . . 351
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 351
Fluid Properties . . . . . . . . . . . . . . . . . . . . . . 351
Gravity . . . . . . . . . . . . . . . . . . . . . . . . . 352

Theory for the Laminar Flow and Creeping Flow Interfaces 354
General Single-Phase Flow Theory . . . . . . . . . . . . . . . 355
Compressible Flow . . . . . . . . . . . . . . . . . . . . . 357
Weakly Compressible Flow . . . . . . . . . . . . . . . . . . 357
The Mach Number Limit . . . . . . . . . . . . . . . . . . . 357
Incompressible Flow . . . . . . . . . . . . . . . . . . . . 358
The Reynolds Number. . . . . . . . . . . . . . . . . . . . 359
Gravity . . . . . . . . . . . . . . . . . . . . . . . . . 360
Theory for the Wall Boundary Condition . . . . . . . . . . . . 361
Prescribing Inlet and Outlet Conditions . . . . . . . . . . . . . 365
Fully Developed Flow (Inlet) . . . . . . . . . . . . . . . . . 367
Fully Developed Flow (Outlet). . . . . . . . . . . . . . . . . 369
No Viscous Stress . . . . . . . . . . . . . . . . . . . . . 370
Normal Stress Boundary Condition . . . . . . . . . . . . . . . 370
Pressure Boundary Condition . . . . . . . . . . . . . . . . . 371
Mass Sources for Fluid Flow . . . . . . . . . . . . . . . . . 373
Numerical Stability — Stabilization Techniques for Fluid Flow . . . . . 375
Solvers for Laminar Flow . . . . . . . . . . . . . . . . . . . 377
Pseudo Time Stepping for Laminar Flow Models . . . . . . . . . . 380
Discontinuous Galerkin Formulation . . . . . . . . . . . . . . 381
Particle Tracing in Fluid Flow . . . . . . . . . . . . . . . . . 382
References for the Single-Phase Flow, Laminar Flow Interfaces . . . . 383

CONTENTS | 13
 Theory for the Darcy’s Law Interface 385
About Darcy’s Law . . . . . . . . . . . . . . . . . . . . . 385
Darcy’s Law — Equation Formulation . . . . . . . . . . . . . . 386
Storage Model . . . . . . . . . . . . . . . . . . . . . . . 387
Average Linear Velocity . . . . . . . . . . . . . . . . . . . 388
References for the Darcy’s Law Interface. . . . . . . . . . . . . 388

Theory for the Free and Porous Media Flow Interface 390
Reference for the Free and Porous Media Flow Interface. . . . . . . 390

Theory for the Brinkman Equations Interface 391

About the Brinkman Equations . . . . . . . . . . . . . . . . 391
Brinkman Equations Theory. . . . . . . . . . . . . . . . . . 391
References for the Brinkman Equations Interface. . . . . . . . . . 393

Theory for the Coupling of Fluid Flow to Electrochemical

Reactions 394

Chapter 7: Heat Transfer

Coupling of Heat Transfer to Electrochemical Reactions 396

Joule Heating Due to Charge Transport . . . . . . . . . . . . . 397
Heating Due to Electrochemical Reactions . . . . . . . . . . . . 397

Chapter 8: Level Set and Phase Field

The Level Set Interface 402

Domain, Boundary, and Pair Nodes for the Level Set Interface . . . . 403
Level Set Model . . . . . . . . . . . . . . . . . . . . . . 404
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 404
Inlet . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
No Flow . . . . . . . . . . . . . . . . . . . . . . . . . 405
Open Boundary . . . . . . . . . . . . . . . . . . . . . . 406
Thin Barrier. . . . . . . . . . . . . . . . . . . . . . . . 406
Continuity . . . . . . . . . . . . . . . . . . . . . . . . 406

14 | C O N T E N T S
 The Phase Field Interface 408
Domain, Boundary, and Pair Nodes for the Phase Field Interface . . . . 409
Phase Field Model . . . . . . . . . . . . . . . . . . . . . 410
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 411
Inlet . . . . . . . . . . . . . . . . . . . . . . . . . . . 412
Wetted Wall . . . . . . . . . . . . . . . . . . . . . . . 412
Interior Wetted Wall . . . . . . . . . . . . . . . . . . . . 413
Continuity . . . . . . . . . . . . . . . . . . . . . . . . 413

Theory for the Level Set Interface 414

The Level Set Method . . . . . . . . . . . . . . . . . . . . 414
Conservative and Nonconservative Form . . . . . . . . . . . . 416
Initializing the Level Set Function . . . . . . . . . . . . . . . . 416
Variables For Geometric Properties of the Interface . . . . . . . . 417
Reference for the Level Set Interface . . . . . . . . . . . . . . 417

Theory for the Phase Field Interface 418

About the Phase Field Method. . . . . . . . . . . . . . . . . 418
The Equations for the Phase Field Method . . . . . . . . . . . . 418
Conservative and Nonconservative Forms . . . . . . . . . . . . 420
Additional Sources of Free Energy . . . . . . . . . . . . . . . 421
Initializing the Phase Field Function . . . . . . . . . . . . . . . 421
Variables and Expressions . . . . . . . . . . . . . . . . . . 422
Reference for the Phase Field Interface . . . . . . . . . . . . . 423

Chapter 9: Multiphysics Coupling Nodes

Deforming Electrode Surface . . . . . . . . . . . . . . . . . 426
Nondeforming Boundary . . . . . . . . . . . . . . . . . . . 427
Electrochemical Heating . . . . . . . . . . . . . . . . . . . 428
Potential Coupling . . . . . . . . . . . . . . . . . . . . . 428
Space Charge Density Coupling . . . . . . . . . . . . . . . . 428
Boundary Electrolyte Potential Coupling . . . . . . . . . . . . . 429

CONTENTS | 15
 Chapter 10: Glossary

Glossary of Terms 432

16 | C O N T E N T S
 1

Introduction

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

for COMSOL Multiphysics®.

This chapter introduces you to the capabilities of this module. 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 Electrodeposition Module

• Overview of the User’s Guide

17
 About the Electrodeposition Module
These topics are included in this section:

• What Can the Electrodeposition Module Do?

• The Electrodeposition Module Physics Interface Guide
• Common Physics Interface and Feature Settings and Nodes
• 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 Electrodeposition Module Do?

The Electrodeposition Module is intended for investigating the influence of different
parameters, in an electrodeposition cell, on the thickness and composition of deposited
layers. Important parameters that can be studied with the module are the following:

• Cell geometry
• Electrolyte composition and mixing
• Electrode kinetics
• Operating potential and average current density
• Temperature

Modeling and simulations are cost-effective ways of understanding, optimizing, and

controlling electrodeposition processes. A typical simulation yields the current
distribution in the electrodeposition cell and at the surface of the electrodes. Faraday’s
law and the properties of the deposited material give the thickness and composition of
the deposited layer. The Electrodeposition Module is able to model cells both when
the deposited thickness is negligible in comparison to the inter-electrode gap and
where the growth and dissolution of the electrodes have to be taken into account using
moving boundaries.

The targeted applications for this module are the following:

• Copper deposition for electronics and electrical applications

18 | CHAPTER 1: INTRODUCTION
 • Metal deposition for protection of parts, such as corrosion protection and
protection against wear
• Decoration of metals and plastic parts
• Electroforming of parts with thin and complex structure
• Metal electrowinning.

The module consists of a number of physics interfaces, which describe different

phenomena in the electrolyte and at the electrodes in electrodeposition cells. A
number of examples exemplify the use of these physics interfaces. The physics
interfaces are based on the conservation of current, charge, chemical species, and
energy.

The Electrodeposition Module Physics Interface Guide

The Electrodeposition 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 Electrodeposition Module are listed in the table. The functionality
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

ABOUT THE ELECTRODEPOSITION MODULE | 19

 PHYSICS INTERFACE ICON TAG SPACE AVAILABLE STUDY TYPE
DIMENSION

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
Chemistry chem all dimensions stationary; time dependent

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
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

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

Current Distribution, cdbem 3D, 2D stationary; stationary with

Boundary Element initialization; time
dependent; time dependent
with initialization; AC
impedance, initial values;
AC impedance, stationary;
AC impedance, time
dependent
Electroanalysis tcd 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
Electrodeposition, Deformed Geometry

Electrodeposition, cd + dg all dimensions stationary; time dependent;

Primary time dependent with
initialization; AC
impedance, initial values;
Electrodeposition, AC impedance, stationary;
Secondary AC impedance, time
dependent
Electrodeposition, tcd + dg all dimensions stationary; stationary with
Tertiary with initialization; time
(Electroneutrality, dependent; time dependent
Supporting Electrolyte) with initialization; AC
impedance, initial values;
AC impedance, stationary;
AC impedance, time
dependent
Fluid Flow

Porous Media and Subsurface Flow

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

axisymmetric

ABOUT THE ELECTRODEPOSITION MODULE | 21

 PHYSICS INTERFACE ICON TAG SPACE AVAILABLE STUDY TYPE
DIMENSION

Darcy’s Law dl all dimensions stationary; time dependent

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

Flow axisymmetric
Nonisothermal Flow

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

axissymmetri stationary, one-way NITF;
c time dependent, one-way
NITF
Fluid-Structure Interaction

Heat Transfer

Heat Transfer in Porous ht all dimensions stationary; time dependent

Media
Mathematics

Moving Interface

Level Set ls all dimensions time dependent with phase

initialization
Phase Field pf all dimensions time dependent; time
dependent with phase
initialization

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.

22 | CHAPTER 1: INTRODUCTION
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 2-4 for

links to common sections and Table 2-5 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.

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
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

ABOUT THE ELECTRODEPOSITION MODULE | 23

 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.

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.

24 | CHAPTER 1: INTRODUCTION
THE APPLICATION LIBRARIES WINDOW
Each model or application includes documentation with the theoretical background
and step-by-step instructions to create a model or application. 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.

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 info@[Link].

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

ABOUT THE ELECTRODEPOSITION MODULE | 25

 support@[Link]. 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 [Link]

Contact COMSOL [Link]/contact
COMSOL Access [Link]/access
Support Center [Link]/support
Product Download [Link]/product-download
Product Updates [Link]/support/updates
COMSOL Blog [Link]/blogs
Discussion Forum [Link]/community
Events [Link]/events
COMSOL Application Gallery [Link]/models
COMSOL Video Gallery [Link]/video
Support Knowledge Base [Link]/support/knowledgebase

26 | CHAPTER 1: INTRODUCTION
Overview of the User’s Guide
The Electrodeposition 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 BEM, Electrode, Shell, and Electroanalysis interfaces.

ELECTRODEPOSITION, DEFORMED GEOMETRY INTERFACES

Electrodeposition, Deformed Geometry Interfaces chapter describes the
Electrodeposition, Primary, Electrodeposition Secondary and Electrodeposition,
Tertiary Nernst-Planck interfaces.

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.

OVERVIEW OF THE USER’S GUIDE | 27

 FLUID FLOW INTERFACES
Fluid Flow Interfaces chapter describes the Darcy’s Law, Free and Porous Media Flow,
and the Brinkman Equations interfaces.

HEAT TRANSFER
Heat Transfer chapter describes how to couple electrochemical heat sources to heat
transfer.

LEVEL SET AND PHASE FIELD

The Level Set and Phase Field chapter describes physics interfaces that can be used for
modeling geometries undergoing topological changes as a result of electrode
deformations.

THE MULTIPHYSICS COUPLING NODES

The Multiphysics Coupling Nodes chapter describes the coupling nodes available
under the Multiphysics node for coupling various electrochemical interfaces using
potential or space charge density couplings, for example.

28 | CHAPTER 1: INTRODUCTION
 2

Modeling with Electrochemistry

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

29
 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 an electrical current is drawn.

30 | 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, for example, when designing a battery 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 electrolytes. 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 | 31

 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
currents 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 an electrolyte solution. 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 transferred 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

32 | 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 cases where more advanced nonlinear charge conservation equations
and concentration-dependent electrode polarization are required, 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 | 33

 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 flowchart for selecting a proper current distribution interface for a

model is shown below. The recommendations here are indicative and the modeler may
sometimes want 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 flowchart 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

34 | 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 | 35

 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, or by using the Tertiary Current Distribution,
Nernst-Planck interface with Charge conservation model: Poisson, 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

36 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

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

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

Clearly, the right-most term is zero: that is, convection of an electroneutral solution
does not cause current flow. The leftmost 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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 37

 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

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.

38 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

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)

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.

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 39

 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

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 m depends on both the electric potential in the electrode φ s and the

electrolyte potential φ l . Where there is substantial resistance to current
flow through a solution, the corresponding potential difference in φ l
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.

40 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

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 expressions is not
general and can never replace experimental kinetic data if such is available.

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.

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 41

 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

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 needs to be set up manually by the Electrode Surface
Couplingnodes. When modeling porous electrodes, the corresponding coupling node
to create a source/sink in 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

42 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

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 m,
the number of electrons transferred in reaction m, in a reductive direction and F the
Faraday constant (96485 C/mol, the absolute charge on a mole of electrons).

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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 43

 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:

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

In this formulation, assuming the stoichiometric coefficients of the oxidized and

reduced species to be -1 and 1, respectively, the exchange current density, i0, is defined
as:

cR αc ⁄ n cO αa ⁄ n
i 0 = i 0, ref ------------- -------------- (2-6)
c R, ref c O, ref

where i0, ref is the exchange current density at some chosen reference conditions, and
the overpotential is defined as

η = E – E eq (2-7)

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

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

and Eeq, ref is the equilibrium potential at the same reference conditions.

Typically standard conditions are used as reference concentrations, for instance

concentrations of 1 M for ions in aqueous solutions.

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 R → 0 ), the factor ln ------ may become 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

44 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

 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

η ref = E – E eq,ref (2-10)

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 | 45

 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

46 | 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 with respect to ground to
control the cell potential, or the Electrode Potential with respect to 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 | 47

 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.

48 | 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 | 49

 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

50 | 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 | 51

 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.

52 | 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 Inspecting and Troubleshooting Meshes
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 | 53

 • 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 too 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

54 | 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 | 55

 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

56 | 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
[Link] 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
[Link] A/m Electrolyte current density in Boundaries to Electrolyte and
normal direction Porous Electrode domains
[Link] A/m2 Electrode current density in Boundaries to Electrolyte and
normal direction Porous Electrode domains

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 57

 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
[Link] 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
[Link] A/m3 Total volumetric current Porous Electrode domains
densities (local sum of all
xxx.iv_yy)
[Link] A/m2 Electrolyte current density Electrolyte domains
magnitude (L2 norm)
[Link] 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 nonlocal
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:

• Nonlocal Couplings and Coupling Operators and Integration

Avoid evaluating the [Link]/[Link] variables on boundaries. These

are generally less accurate than the [Link]/[Link] variables.

58 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

 3

Electrochemistry Interfaces

This chapter describes the physics interfaces and features to model electrochemical
cells. The physics interfaces described are found under the Electrochemistry
branch ( ).

In this chapter:

• The Primary and Secondary Current Distribution Interfaces

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

59
 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
• Thin Electrolyte Layer • Electrolyte Point Current Source
• Edge Electrode

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 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.

60 | 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, except that it also 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.

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 | 61

 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 between Primary or Secondary 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.

PHYSICS VS. MATERIALS REFERENCE ELECTRODE POTENTIAL

The Physics vs. Materials Reference Electrode Potential setting on the physics interface
node can be used to combine material library data for current densities and equilibrium
potentials with an arbitrary reference electrode scale in the physics. The setting affects
the electrode potentials used for model input into the materials node, as well as all
equilibrium potential values output from the materials node.

62 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Note that the setting will only impact how potentials are interpreted in communication
between the physics and the Materials node. If the From material option is not in use
for equilibrium potentials or electrode kinetics, the setting has no impact.

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.

DISCRETIZATION
The interface uses Linear elements by default and this setting is recommended for most
problems. Certain types of problems, such as models using porous electrodes, or
current distribution problems in two dimensions or higher, may benefit in terms of
solution accuracy from using Quadratic elements.

In multiphysics models it is generally recommended to use the same element order in

all coupled interfaces.

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

• 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: Rotating Cylinder Hull Cell:

Application Library path
Electrodeposition_Module/Verification_Examples/rotating_cylinder_hull_cell

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 PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 63

 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.

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.

Note: For Primary current distributions, or for models solved using a Current
Distribution Initialization study step set to Primary, the settings of this section usually
have limited impact on the solver convergence.

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, a current
collector/feeder or a gas diffusion layer (GDL) in a fuel cell — use an Electrode node
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.

64 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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.

The Electrode volume fraction is used to calculate the effective electrical conductivity of
the porous matrix when the correction factor is set to Bruggeman or Tortuosity.
Additionally, it is used in calculating the active specific surface area of the porous matrix
when Particle-based area option is selected in the child nodes.

DISSOLVING-DEPOSITING SPECIES
Use the settings of this section to define species that participate in
dissolution-deposition electrode reactions within the porous electrode, for instance
metal deposition/dissolution or oxide formation.

Use the Add ( ) and Delete ( ) buttons as needed in the tables to control the
number of species.

Dependent variables for the volumetric molar concentration are added for each
dissolving-depositing species. These variables can be used to keep track of the amount
of reacted material in the porous electrode. The total molar dissolution/deposition
rate depends on the reaction rates and stoichiometry, defined in the Porous Electrode
Reaction subnodes.

The Density and Molar mass determine the electrode growth velocity and the resulting
dissolved/deposited layer thickness. By multiplying by the electrode surface area (in
the case of multiple electrode reaction the average surface area is used), the change in
electrode and electrolyte volume fractions can be also be calculated. By use of the Add
volume change to electrode volume fraction (not available for Separator node of Tertiary
Current Distribution interface) and Subtract volume change from electrolyte volume
fraction check boxes you may define how these volume changes should be included in
the model.

Thickness variables, based on the surface area, are also defined that you for instance
can use to couple to the Film Resistance (see below).

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 65

 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.

Use the Apply for electrolyte phase and Apply for electrolyte checkboxes to enable the
periodic condition for the electrolyte and electrode phase potentials, respectively.

By specifying a Potential difference, an offset in potential (typically per unit cell) can be
prescribed.

For more information, see Periodic Boundary Conditions in the COMSOL

Multiphysics Reference Manual.

Thin Electrolyte Layer

The Thin Electrolyte Layer node can be used to model a thin insulating or resistive
sheet, located on an interior boundary in an electrolyte domain. The node can be used
as an alternative to drawing the actual layer domain in the model geometry, which may
significantly reduce meshing and solver time, especially in 3D models.

Thin insulating sheets are commonly inserted in the electrolyte in various types of
electrochemical cells. For example they may be used for optimizing the current
distribution in a corrosion protection application, of for optimizing the local
deposition rate in a deposition bath.

The layer may be set to be either Insulating or Resistive.

For the case of Resistive, the Surface Resistance can either be set directly, or calculated
from Thickness and Conductivity values.

ADVANCED SETTINGS
Enable Slit electric potential in porous electrodes to make the layer fully insulating for
the electrode phase potential along the selected boundaries.

66 | 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.

DISSOLVING-DEPOSITING SPECIES
Use the settings of this section to define species that participate in
dissolution-deposition electrode reactions o n the edge electrode, for instance metal
deposition/dissolution or oxide formation.

Use the Add ( ) and Delete ( ) buttons as needed in the tables to control the
number of species.

Dependent variables for the molar concentration (SI unit: mol/m) are added for each
dissolving-depositing species. These variables can be used to keep track of the amount
of reacted material on the electrode. The total molar dissolution/deposition rate
depends on the reaction rates and stoichiometry, defined in the Electrode Reaction sub
nodes.

The Density and Molar mass determine the electrode growth velocity and the resulting
dissolved/deposited layer thickness, so that the change in the edge electrode radius
also can be calculated. By use of the Add volume change to edge radius check box you
may define if this volume change should be included in the model.

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 67

 A thickness variable is also defined. Use it, for instance, to couple to the Film
Resistance (see below).

Decorative Plating: Application Library path

Electrodeposition_Module/Tutorials/decorative_plating

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 More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

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.

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.

68 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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.

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.

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 69

 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.

Electrode Current
Use this node to define a current source in a point of an Edge Electrode node.

This node is available as a subnode to the Edge Electrode node, when Ohm’s Law has
been selected as the electric potential model.

70 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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

• The Tertiary Current Distribution, • Separator

Nernst–Planck Interface • Reactions
• Electrolyte • Thin Electrolyte Layer
• Porous Electrode • Initial Values

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 Electrolyte Charge Conservation 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

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 71

 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.

ELECTROLYTE CHARGE CONSERVATION

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

72 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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 ([Link]) and hydroxide ([Link]) automatically, and that dependent variables
for these two species should not be added under Dependent Variables below. With this
setting, to control the initial pH in a simulation, set the initial concentrations of the
other ions in the simulation such that the matching concentration of protons and
hydroxide ions matches the pH desired. For pH less than 7, add and set the
concentration of anions. For pH more than 7, add and set the concentration of cations.
For example, for a water-based system with only Cl-, an initial concentration for Cl- of
10-5 M will result in an initial pH of 5. This is analogous to acidifying the solution
using HCl.

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

Use the Electroanalysis (no potential gradients) option to model electroanalytical

problems with electrolyte solutions containing a large quantity of inert supporting
electrolyte, with a conductivity so high that ohmic losses can be assumed to be
negligible. The electroanalysis option will not solve for the electrolyte potential as a
dependent variable, setting it to a constant value of 0. Migration effects are hence
neglected. Domain and boundary nodes only applicable to the electrolyte phase
potential will be disabled when using electroanalysis.

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.

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 73

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

PHYSICS VS. MATERIALS REFERENCE ELECTRODE POTENTIAL

The Physics vs. Materials Reference Electrode Potential setting on the physics interface
node can be used to combine material library data for current densities and equilibrium
potentials with an arbitrary reference electrode scale in the physics. The setting affects
the electrode potentials used for model input into the materials node, as well as all
equilibrium potential values output from the materials node.

Note that the setting will only impact how potentials are interpreted in communication
between the physics and the Materials node. If the From material option is not in use
for equilibrium potentials or electrode kinetics, the setting has no impact.

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 More Options button ( ) and select
Advanced Physics Options from the Show More Options dialog box.

CONSISTENT STABILIZATION AND INCONSISTENT STABILIZATION

To display these sections, click the Show More Options button ( ) and select
Stabilization from the Show More Options dialog box. There are two consistent
stabilization methods available and selected by default — Streamline diffusion and
Crosswind diffusion. There is one inconsistent stabilization method, Isotropic diffusion,

74 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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)/[Link],
where [Link] 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 2-4 for links
to common sections and Table 2-5 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

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.

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 75

 What settings are available in this node depends on the Electrolyte Charge
Conservation 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.

The Water Self-ionization section is available for the Electroneutrality, water-based

option. The section allows the water self-ionization constant to be set. Using the Built
in option, the constant will be set to account for temperature, giving the pH of the
simulation the correct temperature dependence.

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.

76 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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 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.

The Electrode volume fraction is used to calculate the effective electrical conductivity of
the porous matrix when the correction factor is set to Bruggeman or Tortuosity.
Additionally, it is used in calculating the active specific surface area of the porous matrix
when Particle-based area option is selected in the child nodes.

DISSOLVING-DEPOSITING SPECIES
See the Porous Electrode node of The Primary and Secondary Current Distribution
Interfaces.

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

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 77

 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.

DISSOLVING-DEPOSITING SPECIES
See the Porous Electrode node of The Primary and Secondary Current Distribution
Interfaces.

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

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.

78 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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 top node, and adds
a fixed space charge to the electroneutrality condition.

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

Ion Exchange Membrane Boundary

Use the Ion Exchange Membrane boundary node to specify 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 TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 79

 The node is applicable to external boundaries to electrolyte domains. For defining
ion-exchange membranes on an interior boundary between two electrolyte domains,
use the Thin Electrolyte Layer node.

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 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.

Thin Electrolyte Layer

Use this node to specify a thin layer on an interior boundary between two electrolyte
domains. The node can be used as an alternative to drawing the actual layer as a
domain in the model geometry, which may significantly reduce meshing and solver
time, especially in 3D models.

The layer may either be Insulating, Resistive (supporting electrolytes only), or an Ion
exchange membrane.

For Resistive or Ion exchange membrane, the potential drop over the membrane is
determined either from the Surface resistivity or the Thickness and conductivity.

For Ion exchange membrane, the choice of Charge-carrying species concentration species
specifies that the current flowing over the layer will be carried by this species (which
must have a nonzero charge number). 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 User defined.

80 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

The Current Distribution, Boundary
Elements Interface
The Current Distribution, Boundary Elements (cdbem) interface ( ), found under the
Electrochemistry branch ( ) when adding a physics interface, solves for the
electrolyte potential using the Laplace equation. The equations are formulated and
solved for by the use of the Boundary Element Method (BEM). The interface is
available for 2D and 3D components.

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

The individual node settings of the Current Distribution, Boundary Elements are in most
cases identical to the corresponding nodes in The Primary and Secondary Current
Distribution Interfaces. This chapter will only cover features and settings specific for
the Current Distribution, Boundary Elements interface.

The Current Distribution, Boundary Elements Interface

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

DOMAIN SELECTION
The interface supports selection of voids.

When the Infinite void is selected the boundary element formulation includes infinity.
Use the settings of the Infinity Condition section to set the boundary condition for
the potential at infinity.

Note: The default domain selection of the interface is All domains and voids which
includes the Infinite void. The domain number of the infinite void is 0. Another way
to add the Infinite void to the selection is to click Paste Selection and type in 0.

SYMMETRY
Symmetry can be a convenient way to add insulating boundaries of infinite extension,
for instance to model the surface of the ocean in a sub-sea corrosion protection
problem.

THE CURRENT DISTRIBUTION, BOUNDARY ELEMENTS INTERFACE | 81

 Use the applicable combo boxes to activate a symmetry plane in 3D space dimension
and a symmetry line in 2D space dimension and specify the location (x, y, z) of the
plane/line using the Plane position/Line position parameter.

FAR FIELD APPROXIMATION

The BEM problem is solved with Use far field approximation check box enabled and
using an iterative solver by default. The far field approximation in combination with an
iterative solver may in many cases lead to a significantly lower computational load.

INFINITY CONDITION
Use the settings of this section to apply a boundary condition for the electrolyte
potential at infinity.

The settings are only active if the Infinite Void is included in the selection.

QUADRATURE
In this section you can specify the integration orders for different types of elements in
the model. A higher integration order increases the accuracy of the computed results
but can take longer to compute.

All the integration orders should be at least equal to the discretization order of the
dependent variable, but for all but distant elements, higher orders are recommended.
The integration order for Integration order, weak contribution should be at least twice
the discretization order of the dependent variable.

The automatic selection sets the integration orders of all types of elements depending
upon the dependent variable discretization order selected in the Discretization section.
There is also Manual selection option where the integration orders of all types of
elements can be edited.

CURRENT DISTRIBUTION TYPE

The selection from the Current Distribution Type list 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.

82 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

PHYSICS VS. MATERIALS REFERENCE ELECTRODE POTENTIAL
The Physics vs. Materials Reference Electrode Potential setting on the physics interface
node can be used to combine material library data for current densities and equilibrium
potentials with an arbitrary reference electrode scale in the physics. The setting affects
the electrode potentials used for model input into the materials node, as well as all
equilibrium potential values output from the materials node.

Note that the setting will only impact how potentials are interpreted in communication
between the physics and the Materials node. If the From Materials option is not in use
for equilibrium potentials or electrode kinetics, the setting has no impact.

DISCRETIZATION
In this section you can specify the discretization orders of the dependent variable and
of auxiliary boundary element method boundary flux variables.

Note: The discretization order of auxiliary boundary element method edge flux
variables is the same as that of the dependent variable.

Edge Features in 3D for the Current Distribution, Boundary

Elements Interface.
The edge nodes in the interface contain some extra settings compared to the edge
nodes in The Primary and Secondary Current Distribution Interfaces.

When using edge nodes (in 3D) the interface creates virtual tubes around the edge
selections, defined by the Edge radius (m).

It is generally assumed that the edge radius is small in comparison to other geometrical
measures of the model such as the edge length and the distance between different
edges in the geometry. This usually also implies that the decrease of available
electrolyte volume for charge transport, due to the space occupied by the tubes, can
be neglected. Enable Compensate for tube volume to include the effect of the volume
of the tubes on the electrolyte charge transfer.

THE CURRENT DISTRIBUTION, BOUNDARY ELEMENTS INTERFACE | 83

 Note that additional degrees of freedoms are introduced in the model when
compensating for the tube volume, and that this may result in higher memory usage
and longer solver times.

• The Primary and Secondary Current Distribution Interfaces

• Shared Physics Features in the Current Distribution Interfaces
• Theory for the Current Distribution Interfaces

84 | 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
This chapter describes various domain, boundary, edge, point, and pair nodes that are
common to several of the Electrochemistry Interfaces interfaces.

The nodes are 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).The 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 | 85

 • Circuit Terminal • Highly Conductive Porous
• Double Layer Capacitance Electrode

• Electric Ground • Initial Values for

Adsorbing-Desorbing Species
• Electric Potential
• Initial Values for
• Electric Reference Potential
Dissolving-Depositing Species
• Electrode
• Insulation
• Electrode Current
• Perforated Electrode Surface
• Electrode Current Density
• Internal Electrode Surface
• Electrode Current Source
• Line Mass Source1
• Electrode-Electrolyte Boundary
• Non-Faradaic Reactions
Interface
• Point Mass Source1
• Electrode Potential
• Porous Electrode Reaction
• Electrode Reaction
• Porous Matrix Double Layer
• Electrode Surface
Capacitance
• Electrolyte Current Density
• Reference Electrode
• Electrolyte Current Density
• Symmetry
• Electrolyte Current Source
• Thin Electrode Layer
• Electrolyte Potential
• External Short
• Harmonic Perturbation
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 2-4 for links
to common sections and Table 2-5 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

86 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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

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

Highly Conductive Porous Electrode

The Highly Conductive Porous Electrode node defines a charge balance of the pore
electrolyte in a porous electrode, and, for interfaces solving for electrolyte species, the
corresponding mass balance for the species in the electrolyte. Use this node when
electrical conductivity is high enough to assume uniform potential in the electron
conducting phase of the porous electrode.

See the Electrode Surface node for a description of the Electrode Phase Potential
Condition and Harmonic Perturbation sections.

See the Porous Electrode node for a description of the remaining settings.

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.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 87

 To use this feature, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box. 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 More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box. Then add the node from the
Additional Sources submenu.

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.

88 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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.

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

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 89

 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 interior
boundaries between electrolyte and electrode domains, use the Internal Electrode
Surface node. For interior boundaries to electrolyte domains, use the Perforated
Electrode Surface node.

DISSOLVING-DEPOSITING SPECIES
Use the settings of this section to define species that participate in
dissolution-deposition electrode reactions, for instance metal deposition/dissolution
or oxide formation.

Use the Add ( ) and Delete ( ) buttons as needed in the table to control the
number of species.

The Density and Molar mass, in conjunction with the reaction rates and stoichiometry,
defined in the Electrode Reaction subnodes, determine the normal electrode growth
rate. The growth rate can be used in conjunction with the Deforming Electrode
Surface and Nondeforming Boundary multiphysics couplings to model geometry
deformations.

When the Solve for species concentrations variables check box is checked, dependent
variables for the molar surface concentration of the dissolving-depositing species are
added. These can be used to model the thickness of an dissolving/depositing layer in
a time-dependent simulation where the resulting deformation in the model geometry
is small and will have negligible impact on the current distribution. In stationary
studies, the molar surface concentration variables will be defined but not solved for by
default.

90 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

When solving for the species concentration variables, corresponding thickness variables
are defined that you for instance can use to couple to the Film Resistance (see below).

Deposition-Dissolution Rates, Growth Velocities, and Thicknesses on an

Electrode Surface

SPECIES CONSERVATION ON DEFORMING GEOMETRY

In Deforming Geometry simulations, the Compensate for Boundary Stretching adds
a tangential convection term, based on the movement of the mesh, to the mass balance
equations of the dissolving-depositing species surface concentrations.

ADSORBING-DESORBING SPECIES
Use the settings of this section to define species that may adsorb or desorb on the
electrode surface during charge transfer, or non-faradaic, reactions.

The Density of sites parameter will be used to set up the local surface mass balance
equations for the fractional surface coverages.

Use the Add ( ) and Delete ( ) buttons as needed in the table to control the
number of species. The name of each adsorbing-desorbing Species may be edited in the
first column of the table. Use a Site occupancy number larger than unity for species that
occupy more than one site at the electrode surface.

According to the settings of the table, the fractional surface coverage variable names
will be defined according to xxx.theta_yyy_zzz where xxx is the interface name,
yyy the tag of the electrode surface node, and zzz the species name. The variable
xxx.thetafree_yyy represents the fraction of free surface sites. These variable names
may be used when defining kinetics parameters in Electrode Reaction subnodes.

Use The Surface Reactions Interface to model surface diffusion.

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 | 91

 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.

ELECTRODE PHASE POTENTIAL 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.

92 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Cyclic Voltammetry
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.

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

Counter Electrode (Electroanalysis only)

This boundary condition is only available for the Electroanalysis charge conservation
model in the Tertiary Current Distribution, Nernst-Planck (tcd) interface.

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.

See also Counter Electrodes and Overall Charge Balance

ADVANCED CYCLIC VOLTAMMETRY SETTINGS

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

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

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 93

 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.

EQUILIBRIUM POTENTIAL HANDLING (PRIMARY CONDITION)

This setting only has an effect if there are multiple Electrode Reaction subnodes
present and 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.

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

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 More Options button ( ) and
select Advanced Physics Options in the Show More Options dialog box.

• 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.

94 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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

Note that all settings described below are not available for all Electrochemistry
interfaces.

• Electrode Reactions Theory

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

The equilibrium potential may be defined either in the Materials node (From material),
by using the Nernst Equation, or by using a User defined expression.

If the Nernst Equation is used, the concentration dependence is calculated

automatically based on the Reference equilibrium potential Eeq, ref (V).

For all interfaces except the Tertiary Current Distribution interface, the concentration
dependence is based on the user-defined Reduced species expression CR (unitless) and
Oxidized species expression CO (unitless) parameters. CR and CO should be defined so
that the quotient between them is 1 for the reference state (for which Eeq=Eeq, ref).

In the Tertiary Current Distribution interface, the concentration dependence of the

Nernst Equation is based entirely on the settings in the Stoichiometric Coefficients and
the Reference Concentrations sections.

When using Nernst Equation, additional options are available in the Butler-Volmer
expression type in the Electrode Kinetics section.

• Equilibrium Potentials and the Nernst Equation

REFERENCE CONCENTRATIONS
This section is only available in the Tertiary Current Distribution interface, if the
equilibrium potential has been selected to be defined by the Nernst Equation.

The reference concentrations define the reference state for which Eeq = Eeq, ref.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 95

 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.

The Local current density expression, iloc, expr (SI unit: A/m2), may be defined either
in the Materials node (From material), by using the From kinetics expression, or by using
a User defined expression.

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

Most kinetic expression types feature the Limiting Current Density option in order 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).

In the Tertiary Current Distribution interface, the Linearize concentration dependence

for low concentrations option is used to set a Concentration linearization limit clim
(SI unit: mol/m3) for linearizing the concentration dependence of kinetics for low
concentrations, in order to improve convergence for non-unit stoichiometries. Note
that this option is available for Nernst Equation equilibrium potential and Butler-Volmer
kinetics with either Mass action law or Lumped multistep selected as the exchange
current density type.

Butler-Volmer or Linearized Butler-Volmer

The Butler-Volmer kinetics expression is the most common way to define
electrochemical kinetics. 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.

When using the Nernst Equation for defining the equilibrium potential (see above), the
concentration dependence of the Exchange current density i0 may be defined in a
thermodynamically consistent way in accordance with the Nernst equation, in
combination with a Reference exchange current density i0,ref (A/m2), which is the
exchange current density when Eeq=Eeq, ref.

For all interfaces except the Tertiary Current Distribution interface, the concentration
dependence when using From Nernst Equation will use CR and CO as pre-exponential

96 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

factors for the anodic and cathodic terms, respectively. In the Tertiary Current
Distribution interface, the Lumped multistep option can be used to define i0 by the use
of either Generic exponentials, or Anodic or Cathodic reaction orders. The Mass action
law will define the reaction orders according to the reaction stoichiometry and the law
of mass action.

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. In order to ensure thermodynamic consistency, αc cannot be user
defined when i0 is calculated From Nernst Equation (or by Mass action law in the Tertiary
Current Distribution interface). For this case, αc is defined automatically, based on the
and the number of participating electrons in the reaction, defined in the stoichiometry
section.

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.

Concentration Dependent Kinetics

This expression type is not available if Nernst equation has been selected in the
Equilibrium Potential section.

Note that the combination of Nernst equation and the Butler Volmer kinetics type will
in most cases render identical kinetics as for the Concentration Dependent Kinetics. It
is recommended to always use Nernst Equation + Butler Volmer whenever possible,
since this combination is guaranteed to be thermodynamically consistent.

The Concentration Dependent Kinetics expression type may be used in concentration

dependent (tertiary) current distribution problems. One or both of the Oxidizing

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 97

 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.

• Electrode Kinetics Expressions

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.

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:

 νox Sox + ne  νred Sred

-
⇔ (3-1)
ox red

98 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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.

• Mass Fluxes and Sources Due to Electrochemical Reactions

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.

• Heating Due to Electrochemical Reactions

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 99

 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.

Perforated Electrode Surface

The Perforated Electrode Surface is applicable to internal boundaries of an electrolyte
[Link] node may be used to model a thin and highly conductive perforated
(mesh) electrode, immersed in an electrolyte.

Apart from the applicable selection, the node is identical to the Electrode Surface
node.

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

100 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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

The node can only be applied at interior 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 Resistance, Dissolving-Depositing Species and Constraint

Settings sections, see the Electrode Surface node.

• Electrode Reactions Theory

Thin Electrode Surface

Use the Thin Electrode Surface node to define electrode reactions occurring on a thin
electrode, fully immersed in electrolyte. The electrode is assumed to be infinitely thin,
and is only applicable to interior boundaries of electrolyte domains.

The node can be used as an alternative to drawing the actual electrode domain in the
model geometry, and may significantly reduce meshing and solver time, especially in
3D models. The node can typically be used to model electrodeposition or corrosion
processes occurring on thin sheets of metal.

The functionality of the node is similar to the Electrode Surface node. Use the Side
selection setting to define if the electrode reactions, defined by the Electrode Reaction
subnodes, are to be defined Both sides of the electrode, or on the Up or Down side only.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 101

 Upon application of the node, the electrolyte potential dependent variable degree of
freedom is defined as a “slit” with different values on each side on the selected
boundaries. Additional variables defined by the node depending on the electrolyte
potential, also having different values on each side of the internal boundary, are named
using additional u or d postfixes, indicating to which (up or down) side they apply.

The up and down operators in the COMSOL Multiphysics Reference

Manual

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 More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

Electrolyte Current
The Electrolyte Current boundary condition sets the total current or average current
density of a boundary. The condition sets the total inward current without imposing
the current density distribution. 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.

102 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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

• 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.

Thin Electrode Layer

The Thin Electrode Layer node can be used to model a thin insulating or resistive sheet,
located on an interior boundary in an electrode domain. The node can be used as an
alternative to drawing the actual layer domain in the model geometry, which may
significantly reduce meshing and solver time, especially in 3D models.

A thin electrode layer can be used to model, for instance, a contact impedance between
two electronic conductors.

The layer may be set to be either Insulating or Resistive.

For the case of Resistive, the Surface Resistance can either be set directly, or calculated
from Thickness and Conductivity values.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 103

 ADVANCED SETTINGS
Enable Slit electrolyte potential in porous electrodes to make the layer fully insulating
for the electrolyte phase potential along the selected boundaries.

Thin Insulating Layer Theory

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 More Options button ( ) and then select
Advanced Physics Options in the Show More Options dialog box. 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. It is also available and described here for the
Electrodeposition and Deformed Geometry interfaces.

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.

104 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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 More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

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 More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

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.

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.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 105

 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 inward 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 More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

• 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

106 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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 More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

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).

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 107

 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 .

Initial Values for Adsorbing-Desorbing Species

The node sets the initial values for the surface coverage of adsorbing-desorbing species
dependent variables.

This node is available as a subnode for the Electrode Surface, Perforated Electrode
Surface and Internal Electrode Surface. The node is not available if no
adsorbing-desorbing species are present in the parent node.

Initial Values for Dissolving-Depositing Species

The node sets the initial values for the dissolving-depositing surface concentrations
dependent variables.

This node is available as a subnode for the Internal Electrode Surface and
Electrode-Electrolyte Boundary Interface. The node is not available if no
dissolving-depositing species are present or if the Solve for dissolving-depositing species
concentrations check box is cleared in the parent node.

Non-Faradaic Reactions
Use the Non-Faradaic Reactions node to define the reaction rate for
dissolving-depositing species due to non-faradaic (not electrochemical) reactions that
occur on the boundary.

This node is available as a subnode to an Electrode Surface if there are

dissolving-depositing species present in the parent node.

108 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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

Circuit Terminal
This feature is only available with an AC/DC Module or a Battery Design Module
license.

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

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 109

 T he E le c t r o de , S h el l In t erfac e
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.

110 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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 More Options button ( ) and select
Advanced Physics Options in the Show More Options dialog box.

• 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 2-4 for links
to common sections and Table 2-5 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.

Electrodeposition on a Resistive Patterned Wafer: Application Library

path Electrodeposition_Module/Tutorials/resistive_wafer

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.

THE ELECTRODE, SHELL INTERFACE | 111

 These physics nodes are described in this section:

• Boundary Current Source • Electric Potential

• Current Source • External Current Density
• Depositing Electrode • Ground
• Electrode • Initial Values
• Electric Insulation • 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 2-4 for links
to common sections and Table 2-5 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 Full depending on the properties

112 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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.

Depositing Electrode
The Depositing Electrode node implements Equation 3-7 (with no source term),
Equation 3-8, and Equation 3-9. Use this node to define the seed layer thickness, the
electrode thickness change, the electrical conductivity, and the electrode current
density.

The electrode thickness change and electrode current density are typically coupled to
an Electrochemistry interface that describes the current distribution in the adjacent
domain and the electrode reactions.

DEPOSITING ELECTRODE
The Seed layer thickness s0 (SI unit: m) defaults to 1·10-4 m.

Enter a value or expression for the Electrode thickness change Δs (SI unit: m). The
default is 0 m.

The default Electrical conductivity σ (SI unit: S/m) uses the value From material. For
User defined select Isotropic, Diagonal, Symmetric, or Full depending on the properties
of the pore electrolyte. Then enter any expression for the conductivity as a function of
temperature. Then enter a value or expression in the field or matrix.

THE ELECTRODE, SHELL INTERFACE | 113

 ELECTRODE CURRENT DENSITY
Enter a value or expression for the Electrode current density in (SI unit: A/m2). The
default is 0 A/m2.

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 3-7. 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.

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.

114 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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 .

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 More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

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 .

THE ELECTRODE, SHELL INTERFACE | 115

 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 More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

116 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

The Electroanalysis Model Wizard
Entry
The Electroanalysis (tcd) ( ) model wizard entry, found under the Electrochemistry
branch ( ) adds a Tertiary Current Distribution, Nernst-Planck interface to the model
with the Electrolyte Charge Conservation Model set to Electroanalysis by default.

The Electroanalysis option is suitable for modeling mass transport of diluted species in
electrolytes using the diffusion-convection equation, solving for electroactive species
concentration(s).

The Tertiary Current Distribution, Nernst-Planck Interface also features options for
modeling cyclic voltammetry and electrochemical impedance spectroscopy.

Use this model wizard entry to model electroanalytical problems with electrolyte
solutions containing a large quantity of inert “supporting” electrolyte. Ohmic loss is
assumed to be negligible.

The model wizard entry is available 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 and the electric potential, phis, which is solved
for either in the Electrode or Porous Electrode domain feature.

• The Tertiary Current Distribution, Nernst-Planck Interface

• Introduction to Electrochemistry Modeling
• Theory for Electroanalysis

THE ELECTROANALYSIS MODEL WIZARD ENTRY | 117

 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
• Deposition-Dissolution Rates, Growth Velocities, and Thicknesses on an Electrode
Surface
• Stoichiometric Coefficients for Double Layer Capacitive Charging
• 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

118 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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

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 l 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

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 119

 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.

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 the theory for porous

electrodes 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

120 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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.

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  

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 121

 where iloc,m denotes the local charge transfer current density for reaction m, i0 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.

Both the exchange current density and the overpotential are typically
concentration dependent. It is possible include the dependence of
kinetics on concentration in the expression above. It also possible to use
other kinetics expressions.

See Equilibrium Potentials and the Nernst Equation and Electrode

Kinetics Expressions.

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.

122 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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

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:

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 123

  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.

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. See The
Butler-Volmer Equation.

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 loc, m
Ni =  --------------------------
nm F
-
m

where iloc, m 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

124 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Faraday constant. Note that iloc, m denotes the current density perpendicular to the
electrode surface.

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

where av,m (SI unit: m2/m3) is the specific surface area.

Deposition-Dissolution Rates, Growth Velocities, and Thicknesses on

an Electrode Surface
The rate of dissolution or deposition on due to an electrode reaction is defined based
on the reaction stoichiometry, νi,m, and the local current density, iloc,m, as described
in Mass Fluxes and Sources Due to Electrochemical Reactions.

If the reaction rate is known, the total growth vdep, tot (m/s) is defined as the sum of
the velocity contributions for all species and electrode reactions according to:

Mi ν i, m i loc, m
v dep, tot =  ------
ρi  nm F
- -------------------------- (3-3)
i m

Where Mi (SI unit: kg/mol) is the molar mass and ρi (SI unit: kg/m3) the density of
the species. (i is the species index, and m the index of the electrode reaction).

This velocity may be used in deforming geometry models as a boundary condition for
the geometry deformation by assuming that dissolution or deposition always occurs in
the normal direction to an electrode boundary, with the velocity being directed into
the electrolyte domain:

∂x
⋅ n = v dep, tot
∂t

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 125

 In a time-dependent simulation one may also introduce a surface concentration
variable, cs,i (mol/m2) on the boundary and calculate the accumulated surface
concentration change by using a local ordinary differential equation (ODE):

dc s, i ν i, m i loc, m
dt
=  -------------------------
nm F
-
m

The total deposited thickness stot(m) can then be defined as

Mi
s tot =  ------
-c .
ρ i s, i
i

Stoichiometric 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.

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

126 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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 (SI unit: S/m) of the film.

Equilibrium Potentials and the Nernst Equation

Consider an arbitrary, possibly multi-electron step, redox reaction involving a number
of species Si defined as

 
-
ν i S i + ne ↔ νi Si
i:ν i < 0 i:ν i > 0

where νi is the stoichiometric coefficient of the reacting species of index i and n is the
number of participating electrons.

The equilibrium potential of the electrode reaction, Eeq (V), is the electrode potential
(the difference between the electrode phase and electrolyte phase potentials, φ s – φ l )
for which the net reaction rate (and the local current density, iloc) is zero.

The equilibrium potential is directly related to the change of Gibbs free energy of the
reacting species, ΔG, as

ΔG
E eq = – --------
nF

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 127

 Since the free energy of the reacting species is concentration dependent, also the
equilibrium potential is concentration (activity) dependent. Eeq is usually defined
according to the Nernst equation as

ai νi
∏  ------------
RT
E eq = E eq, ref – -------- ln
nF a i, ref
i

where Eeq, ref (V) is the equilibrium potential for a reference state for which all species
activities ai (unitless) are equal to a chosen set of reference activities ai, ref (unitless).

For ideal solutions, the activities are replaced by concentrations. Standard conditions
correspond to reference concentrations of 1M for soluble species in the electrolyte,
partial pressures of 1 atm for gaseous species. Constant activities of 1 is used for solid
(metal) species and solvents.

Electrode Kinetics Expressions

A number of different analytical expressions for the current density perpendicular to
the electrode surface, iloc,m, are available. In the following paragraphs, 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. For an electrode reaction, the activation overpotential,
denoted η (V), is the following:

η = φ s – φ l – E eq

where Eeq denotes the equilibrium potential.

THE BUTLER-VOLMER EQUATION

A common expression for the current density as a function of the activation
overpotential, in modeling of electrochemical systems, is the Butler-Volmer equation:

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

where αc (unitless) denotes the cathodic charge transfer coefficient, αa (unitless) the
anodic charge transfer coefficient, and i0 (SI unit: A/m2) is the exchange current
density.

128 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

It should be noted that, although used extensively for all sorts of reactions in the
electrochemical community, the Butler-Volmer equation was originally derived for
single-electron transfer reactions (for instance implying that the reaction does not
involve the breaking or creation of a chemical bond).

Concentration Dependence and the Exchange Current Density

The exchange current density is generally concentration dependent. For certain
conditions, it is possible to derive analytical expressions for i0. Assuming a
concentration dependent equilibrium potential defined by the Nernst equation (see
previous section Equilibrium Potentials and the Nernst Equation), the kinetics to
follow the law of mass action, and the condition that αa + αc = n, then the exchange
current density becomes as follows:

αc νi –αa νi
---------
- --------------
ai 
 ------------
n ai 
 ------------
n
i 0 = i 0, ref   a i, ref   a i, ref
i:ν i > 0 i:ν i < 0

where i0, ref is the exchange current density (SI unit: A/m2) at the reference state. The
above expression can be derived from the mass action law, which gives the following
expression for the local current density:

 ai  νi
 ------------ α a Fη ref ai  –νi – α c Fη ref 
- exp  --------------------  ------------ exp  ----------------------- 
i loc = i 0, ref 
   a i, ref  RT 
- –
  a i, ref
-
RT 
i:ν i > 0 i:ν i < 0

where the overpotential ηref (SI unit: V) is measured using relative to a reference state,
which yields:

η ref = φ s – φ l – E eq, ref .

This latter form of the Butler-Volmer equation, where the concentration overpotential
and the exchange current density are related to the same reference state, is less error
prone and preferable in a modeling context.

The law of mass action is not always the most practical way for treating complex
reactions involving multiple electron steps. For certain multi-electron reactions, where
one electron transfer step is rate limiting, it is possible to derive a lumped
Butler-Volmer expressions using the following relation for the exchange current
density (see Ref. 1):

ai γi
i 0 = i 0, ref   ------------
a i, ref
-
i

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 129

 where γi are generic exponential coefficients. For this case, αa and αc may be
independently defined. By rearranging the Butler-Volmer expression using ηref
similarly to what was done for the mass action law case above, the γi coefficients relate
to the anodic, ξa,i, or cathodic, ξc,i, reaction orders according to

αa νi
ξ a, i = γ i + -----------
n

and

αc νi
ξ c, i = γ i – ----------- .
n

Exchange Current Density and Rate Constants

In electroanalysis, one commonly defines electrode kinetics in terms of rate constants
rather than exchange current densities.

For instance, for a one electron redox couple of concentrations co and cr, with the same
reference concentration cref for both species, and i0, ref = k0Fcref, the mass action law
expression above 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.

Generic Concentration Dependent Butler-Volmer Type Kinetics

This expression type gives more freedom for the user to define concentration
dependent Butler-Volmer types of expressions, where the anodic and cathodic terms
of the current density expression, typically depending on the local concentrations of
the electroactive species at the electrode surface, may be individually defined:

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

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

reduced and oxidized species in the reaction. Note that if CO ≠ CR when η = 0, this
kinetics expression results in iloc ≠ 0, thus violating the concept of equilibrium. This
may result in thermodynamical inconsistencies, for instance when coupling an
electrochemical model to heat transfer.

130 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

SIMPLIFICATIONS OF THE BUTLER-VOLMER EQUATION

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

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. Aa relates to the corresponding
transfer coefficient as follows

RT ln 10
A a = ----------------------
αa F

The cathodic Tafel expression is defined according to:

η ⁄ Ac
i loc = – i 0 ⋅ 10

where the sign accounts for the negative cathodic charge transfer current. Here, Ac is
required to be negative and relates to the transfer coefficient according to

RT ln 10
A c = – ----------------------
αc F

LIMITING CURRENT DENSITY

The steady-state rate of electrode reactions can never exceed 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 in

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 131

 concentration dependence of the equilibrium potential and the exchange current
density as described above.

When not explicitly including mass transfer in the domain equations one can still
include the effect of transport limitations 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, resulting in the following
kinetics expression:

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 high overpotentials so that either the anodic or an cathodic term
in the Butler-Volmer equation may be neglected.

LINEARIZE CONCENTRATION DEPENDENCE FOR LOW CONENTRATIONS

Consider a concentration-based kinetic expression

dc ν
= r = – kc
dt

where ν and k are positive numbers and the desired behavior is that the rate r and the
concentration c should equal zero in the converged solution at infinite time. However,
if c, due to numerical fluctuations in the solver process, becomes negative during
iterating, issues may arise.

First consider the case when ν equals 1 (or any odd positive integer). Negative values
of c will then cause the rate to become positive, resulting in a “self stabilizing” situation
where c will be approaching 0 with time.

A second case to consider is when ν is an even integer larger than 1. The rate then will
become increasingly negative for negative values of c, resulting in an “exploding”
solution, iterating c towards minus infinity. The standard solution for these cases,
which also works for non-integer ν's larger than 1, is to change the expression c in the
rate term to max(c,eps), where eps is a small number. This will avoid the “exploding”
behavior, but result in poor convergence rate for negative c values since the Jacobian
of the rate with respect to c then becomes zero for negative c's.

132 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

The third case is when ν is a non-integer between 0 and 1. Note now that Jacobian
with respect to c of the rate expression now contains cν−1, which will approach minus
infinity when c approaches zero from the positive side. This may result in poor
convergence, and the max() wrapping will not improve convergence in this case.

The solution for the third case is to linearize the concentration dependence for low
concentrations, that is, to use

ν
r = – kc c > c lim

υ–1
r = – kcc lim c < = c lim

which results in the desired convergence behavior for low and negative concentrations.
Note however that the linearization may result in thermodynamic inconsistencies so
that, for instance, relations like the Nernst equation for the equilibrium potential are
no longer fulfilled. The linearization may also improve convergence of the second case
above.

Theory for Specific Current Distribution Feature Nodes

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

∇ ⋅ 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.

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 133

 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
electrode, the domain equations are the following:

∇ ⋅ i l = A v i loc
∇ ⋅ i s = – A v i loc

where Av denotes the specific surface area (dimension L2/L3), and iloc the local
current density defines the rate of the charge transfer reactions, for instance according
to the Butler-Volmer equation. For various ways of defining iloc see Electrode Kinetics
Expressions.

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

134 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

means that the local current density 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

il ⋅ n =  iloc, m
m

is ⋅ n = –  iloc, m
m
2
where iloc,m (A/m ) 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

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 135

 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 potential of the electron
conducting (metal) phase.

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:

136 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

  il ⋅ 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:

 is ⋅ n ds = I n, s
∂Ω

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:

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 137

 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.

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.

138 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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.

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
zi F c i, 2

which may be rearranged to

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 139

 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:

n ⋅ I l, 1 = n ⋅ I l, 2

THIN INSULATING LAYER THEORY

The usual approach to adding an insulating body in a model is to add a domain to the
geometry and then exclude this domain from the electrolyte. An insulating boundary
condition on the boundaries of the insulating body is then used according to

n ⋅ Il = 0

If the model also includes mass transport, no flux conditions are also used for each
species on the insulation boundaries.

n ⋅ Ji = 0

Introducing very thin domains in the model geometry may however cause issues with
meshing and significantly increase the memory requirements during solving because
the thin thicknesses of the layers need to be resolved in the mesh.

As an alternative to describing the thin layers as domains in the geometry, the Thin
Insulating Layer feature instead models the thin layer as a boundary — that is, a layer
of infinitely small thickness — and then mathematically “slits” the dependent variables.
The slitting implies that separate degrees of freedoms are used on each side on the
boundary. The same boundary conditions as above are then used on each side of the
boundary.

References
1. J. O’M. Bockris, A.K.N. Reddy, and M. Gamboa-Aldeco, Modern Electrochemistry,
vol. 2A, 2nd ed., ch. 7, sec. 7.6, Kluwer Academic/Plenum Press, New York, 2000.

140 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 141
 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 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 [Link]
(domain, Joule heating and porous electrode reactions) and [Link] (boundary,
electrode surface reactions), where xxx is the electrochemistry interface identifier.

• Electrochemistry Interfaces
• Multiphysics Coupling Nodes

142 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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 ) (3-4)

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 (3-5)
 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 3-5 may now be rearranged into

TΔS m
Q m =  η m, tot + ---------------- i m (3-6)
 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 3-5 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

THEORY FOR ELECTROCHEMICAL HEAT SOURCES | 143

 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.

144 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

THEORY FOR ELECTROCHEMICAL HEAT SOURCES | 145
 Theory for the Electrode, Shell
Interface
The Electrode, Shell Interfacedefines electrode current conduction in 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 (3-7)

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 (3-8)

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

146 | 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 (3-9)

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 | 147

 Theory for Electroanalysis
The theory related to the Electroanalysis charge conservation model in The Tertiary
Current Distribution, Nernst-Planck Interface (tcd) is described in this section:

• Electroanalytical Methods
• Supporting Electrolyte
• Domain Equations for the Electroanalysis Case
• Electrode Boundary Conditions in the Electroanalysis Model
• 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.

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

148 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

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
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 other charge conservation models
should be used instead of the Electroanalysis option.

Domain Equations for the Electroanalysis Case

The Electroanalysis option 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 .

THEORY FOR ELECTROANALYSIS | 149

 This is equivalent to the assumption of infinite electrolyte conductivity. Therefore the
Electroanalysis option 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 (3-10)

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 (3-11)
∂t

The Electroanalysis charge conservation model solves Equation 3-10 and

Equation 3-11 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:

∂c i 2
= Di ∇ ci (3-12)
∂t

150 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

Equation 3-12 is Fick’s second law of diffusion.

The Electroanalysis charge conservation model 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 electroneutrality model in Tertiary Current Distribution,
Nernst–Planck interface.

You can also 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

Electrode Boundary Conditions in the Electroanalysis Model

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 ( φ l = 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 ELECTROANALYSIS | 151

 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
- (3-13)
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 transferred electrons. 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 (3-14)

Equation 3-13 and Equation 3-14 constitute the coupling between charge balance
and mass balance. This coupling only applies at the electrode–electrolyte interface,
which is a boundary to the domain where the electroanalysis charge conservation
model 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:

152 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES

 I total =  itotal ds
∂Ω

Domain Equations for the Electroanalysis Case

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  -----------------  (3-15)
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 3-15 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 ELECTROANALYSIS | 153

 Counter Electrodes and Overall Charge Balance
The Electroanalysis charge conservation model 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, φ s, CE, and then solve for this potential to fulfill
the following current balance over all electrode surfaces:

φ s, CE :  i tot dS = 0 (3-16)
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 (3-17)

Note that only one counter electrode potential degree of freedom is added in the
model, regardless of the number of counter electrodes that are active.

Domain Equations for the Electroanalysis Case

154 | 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 (3-18)

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 3-18 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 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 | 155

 φ s, ref = φ l + E eq, ref (3-19)

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 (3-20)

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 (3-21)

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 3-19. 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 3-20, is also defined in all electrode domains.

156 | 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 3-20, 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 3-21. 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 3-20, is also defined on these
features.

ELECTRODE POTENTIALS AND REFERENCE ELECTRODES | 157

158 | CHAPTER 3: ELECTROCHEMISTRY INTERFACES
 4

Electrodeposition, Deformed Geometry

Interfaces

This chapter describes the physics interfaces found under the

Electrochemistry>Electrodeposition, Deformed Geometry branch ( ).

In this chapter:

• About the Electrodeposition, Deformed Geometry Interfaces

159
 About the Electrodeposition,
Deformed Geometry Interfaces
The Electrodeposition, Primary ( ), the Electrodeposition, Secondary ( ) and the
Electrodeposition, Tertiary Nernst-Planck ( ), found under the
Electrochemistry>Electrodeposition, Deformed Geometry branch ( ) in the Add
Physics menu, are predefined multiphysics interfaces for time-dependent modeling of
deformations that occur as a result of deposition and dissolution processes in
electrochemical cells.

Use these physics interfaces to investigate geometrical changes in electrodeposition

cells.

By choosing one of the above multiphysics interfaces, the corresponding Current

Distribution interface and a Deformed Geometry interface are added to the component.
Deforming Electrode Surface and Nondeforming Boundary multiphysics coupling nodes
that couple electrode reactions to boundary velocities are also added by default. The
predefined couplings are set up so that the deforming geometry velocity is set to the
total depositing velocity on boundaries where deposition/dissolution processes occur,
and zero on all other boundaries.

Note that is also possible to extend an already existing current distribution model to
include electrode deformations by manually adding a Deformed Geometry interface
and the required Multiphysics coupling nodes.

• The Primary and Secondary Current Distribution Interfaces

• The Tertiary Current Distribution, Nernst-Planck Interface
• The Deformed Geometry Interface in the COMSOL Multiphysics
Reference Manual
• The Multiphysics Branch in the COMSOL Multiphysics Reference
Manual
• Deforming Electrode Surface multiphysics coupling node
• Nondeforming Boundary multiphysics coupling node

160 | CHAPTER 4: ELECTRODEPOSITION, DEFORMED GEOMETRY INTERFACES

Modeling Deformation of an Electrode Surface
The deposition rate and electrode growth velocity are defined by the Current
Distribution interface by the use of an Electrode Surface (applicable to external
boundaries to an Electrolyte domain) or an Internal Electrode Surface (applicable to
interior boundaries between an Electrolyte and an Electrode domain).

Use the Dissolving-Depositing species section in the Electrode Surface node to specify
what species are participating in the electrode reactions, and use the Electrode
Reaction sub nodes to specify the reaction kinetics and stoichiometry.

An arbitrary number of dissolving-depositing species can be added on an electrode

surface. The surface concentration variables of the deposited species can be used to
calculate the thickness of the deposited layer, and the depositing rate is used to set the
boundary velocity for the deforming geometry.

Dissolution or deposition is always assumed to occur in the normal direction to an

electrode boundary, with the velocity being directed into the electrolyte domain:

∂x
⋅ n = v dep, tot (4-1)
∂t

where vdep, tot is the total growth velocity, defined as the sum of the velocity
contributions for all species and electrode reactions according to:

Mi ν i, m i loc, m
v dep, tot =  ------
ρi  nm F
- -------------------------- (4-2)
i m

Where Mi (SI unit: kg/mol) is the molar mass and ρi (SI unit: kg/m3) the density of
the species.

The boundary condition is implemented similarly to the Normal Mesh Velocity

boundary node in the Deformed Geometry interface.

Tangential Velocities at the Intersection Between a Depositing and a

Nondepositing Boundary
Shared points (in 2D) or edges (in 3D) between depositing and nondepositing
boundaries are handled specifically in the Electrodeposition interfaces.

The deformation in the normal direction of a nondepositing boundary is set to zero at

all times. However, for the deformation velocity of the shared points/boundaries in

ABOUT THE ELECTRODEPOSITION, DEFORMED GEOMETRY INTERFACES | 161

 the tangential direction of the nondepositing boundary, special conditions apply.
These conditions can be derived expressions by assuming growth or dissolution to
occur only in the normal direction of the depositing boundary by addition or removal
of spherical particles (for example metal atoms), see Figure 4-1 below.

Nondepositing material

Electrolyte

Electrode

Nondepositing material

Figure 4-1: Gray/Black arrows in whole stroke indicate the tangential electrode
growth/dissolution velocities, vt, point, at the three-phase intersections between an
electrolyte, a deposition or dissolution electrode and a nondepositing material. Dashed
arrows are the growth or dissolution velocities, vdep, based on the electrodeposition rate
expressions. Note that the tangential velocities depend on both the angle between the
depositing surface and the nondepositing surface, as well as the direction of the normal
velocity.

In the following, the boundary tangents are denoted by t (pointing from electrolyte
to electrode) and the normal by n (pointing in the direction out from the electrolyte
domain).

If the angle between the depositing boundary and the nondepositing boundary is
larger than π, the tangential velocity is set to zero:

if ( t nondep ⋅ n dep < 0 ) v t, point = 0 (4-3)

Otherwise (that is, if the angle between the depositing boundary and the
nondepositing boundary is less than π), the following expressions are used:

Case 1: if v dep n nondep ⋅ n dep > 0 v t, point = v dep ⁄ ( t nondep ⋅ n dep )

(4-4)
Case 2: if v dep n nondep ⋅ n dep < 0 v t, point = v dep ( t nondep ⋅ n dep )

162 | CHAPTER 4: ELECTRODEPOSITION, DEFORMED GEOMETRY INTERFACES

Note that Case 2 above results in a lower velocity in the normal direction of the
depositing surface than the deposition velocity, and that this acts toward forming a π/2
angle between the depositing and the nondepositing boundary, a phenomena
observed in experiments (Ref. 1).

In the Electrodeposition Interfaces, on shared points(2D) and edges(3D) between a

Nondeforming Boundary and Deforming Electrode Surface, the velocity of the
depositing boundary is set according to the expressions above.

REFERENCE
1. J. Deconinck, “Mathematical Modeling of Electrode Growth”, J. Applied
Electrochemistry, vol. 24, pp. 212–218, 1994.

ABOUT THE ELECTRODEPOSITION, DEFORMED GEOMETRY INTERFACES | 163

164 | CHAPTER 4: ELECTRODEPOSITION, DEFORMED GEOMETRY INTERFACES
 5

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

165
 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.

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. Both
constant and varying thicknesses are supported. The value of this parameter is used,
among other things, to automatically calculate molar flow rates from the total molar
flux.

166 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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. Both constant and
varying areas are [Link] value of this parameter is used, among other things,
to automatically calculate molar flow rates from the total molar flux. The default is 1
m2.

TRANSPORT MECHANISMS
Mass transport due to diffusion is always included. Use the check boxes available under
Additional transport mechanisms to control other transport mechanisms.

Note: Some of the additional transport mechanisms listed below are only available in
certain products. For details see [Link]

• 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 [Link]
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:

• Porous Medium
• Unsaturated Porous Medium
• Porous Electrode Coupling
• Volatilization
• Species Source

Note: Mass transport in porous media is only available in a limited set of

add-on products. See [Link]
specifications/ for more details on availability.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 167

 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)/[Link], where [Link]
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 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. See Convective Term Formulation for more
information.

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

The Compute boundary fluxes check box is activated by default so that COMSOL
Multiphysics computes predefined accurate boundary flux variables. When this option

168 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

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 | 169

 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 2-4 for
links to common sections and Table 2-5 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
Medium 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 Medium and Unsaturated Porous Medium nodes,
which add the equations for the species concentrations and provide an interface for
defining the properties of the porous media, as well as additional properties governing

170 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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 Medium, 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

• Mass Balance Equation for Transport of Diluted Species in Porous

Media
• 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: [Link]
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, point,
and pair nodes, listed in alphabetical order, available from the Physics ribbon toolbar

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 171

 (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.
• Contextual subnodes (attributes) are available by clicking the parent
node in the Model Builder, and then selecting the subnode from the
Attributes menu.

172 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

• Adsorption • Periodic Condition
• Concentration • Point Mass Source
• Continuity on Interior Boundaries • Porous Matrix
• Dispersion • Porous Medium
• Electrode Surface Coupling • Porous Electrode Coupling
• Equilibrium Reaction • Reaction Coefficients
• Fast Irreversible Surface Reaction • Reactions
• Fluid • Species Source
• Flux • Surface Reactions
• Flux Discontinuity • Surface Equilibrium Reaction
• Fracture • Symmetry
• Gas • Thin Diffusion Barrier
• Inflow • Thin Impermeable Barrier
• Initial Values • Transport Properties
• Line Mass Source • Unsaturated Porous Medium
• Liquid • Volatilization
• Mass-Based Concentrations
• No Flux
• Open Boundary
• Out-of-Plane Flux
• Outflow
• Partition Condition

Some features require certain add-on modules. For details see https://
[Link]/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.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 173

 In the COMSOL Multiphysics Reference Manual, see Table 2-4 for links
to common sections and Table 2-5 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.

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
Use this section to specify diffusion coefficients describing the diffusion of each species
in the solvent fluid.

Use the Source list to select to pick up diffusion coefficients defined in a material or a
Chemistry interface.

174 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

Select Material, and a Fluid material to use a diffusion coefficient in a material available
in the model. User-defined property groups including a diffusion coefficient output
property are available for selection in the Fluid diffusion coefficient list.

Select Chemistry to use a diffusion coefficient from a Chemistry interface added to

model component. Diffusion coefficients are automatically defined when Calculate
transport properties is selected on the interface level of a Chemistry interface. All
defined diffusion coefficients are available for selection in the Fluid diffusion coefficient
list.

For User defined, enter a value or expression for the Fluid diffusion coefficient Dc of each
species in the corresponding input field. This can be a scalar value for isotropic
diffusion or a tensor describing anisotropic diffusion. Select the appropriate tensor
type — Isotropic, Diagonal, Symmetric, or Full 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: https:/
/[Link]/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 Full —
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.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 175

 Note that the migration in electric fields feature is only available in some COMSOL
products. See details: [Link]

EXAMPLE MODELS

• Separation Through Dialysis: Application Library path

Chemical_Reaction_Engineering_Module/Mixing_and_Separation/dialysis
Web link: [Link]
separation-through-dialysis-258

• Transport in an Electrokinetic Valve: Application Library path

Microfluidics_Module/Fluid_Flow/electrokinetic_valve
Web link: [Link]

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.

176 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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
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 [Link] 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.)

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 177

 • 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: [Link]
fine-chemical-production-in-a-plate-reactor-8589

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 solid walls where no surface
reactions occur. The condition applied for each species corresponds to

– n ⋅ ( – D∇c ) = 0

where n denotes the outward pointing normal of the boundary. When the mass
transport includes migration of ionic species, the no flux condition is:

– n ⋅ ( – D∇c – zu m Fc∇φ ) = 0

CONVECTION
By default, the feature prescribes a vanishing flux due to diffusion and migration in an
electric field. This is the appropriate no flux condition when the relative convective
velocity at the boundary is zero. When the fluid velocity at the boundary is not equal
to that of the boundary, it is often convenient to prescribe the total flux including the
convection. To do this select Include in the Convection section.

When including the convection, the no flux condition prescribed is

– n ⋅ ( – D∇c + uc ) = 0

178 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

or

– n ⋅ ( – D∇c – zu m Fc∇φ + uc ) = 0

when migration of ionic species is included.

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

The option Concentration constraint constrains the concentration values on the
boundary by the use of pointwise constraints.

The other option, Flux (Danckwerts) can be used when the concentration at the
boundary is not known, or when it varies in a non-trivial manner. This may, for
example, be useful when reactions with high reaction rates occur in the vicinity of the
inlet. In this case the concentration far upstream of the boundary is instead prescribed.
The Flux (Danckwerts) condition prescribes the total flux defined by the upstream
concentration and the fluid velocity at the boundary.

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.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 179

 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 field) 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 molar flux across a boundary. The flux can
for example occur due to chemical reactions or a phase change at the boundary. The
flux can also represent the transport to or from a surrounding environment currently
not included model.

The prescribed flux of a species c is by default defined as

– n ⋅ ( – D∇c ) = J 0

180 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

where n denotes the outward pointing normal of the boundary. When the mass
transport includes migration of ionic species, the flux is defined as:

– n ⋅ ( – D∇c – zu m Fc∇φ ) = J 0

The flux prescribed, J0, can include any arbitrary user-specified expression. It can be
constant or a function of a dependent variable or independent variable. Common
examples are a flux dependent of the concentration, temperature, pressure or the
electric potential φ .

CONVECTION
By default, the flux due to diffusion and migration in an electric field is prescribed. This
is the appropriate flux condition when the relative velocity at the boundary is zero.
When the fluid velocity is not equal to that of the boundary, it is often convenient to
prescribe the total flux, including the convection. To do this select Include in the
Convection section.

When including the convection, the prescribed flux is defined as:

– n ⋅ ( – D∇c + uc ) = J 0

or

– n ⋅ ( – D∇c – zu m Fc∇φ + uc ) = J 0

when migration of ionic species is included.

INWARD FLUX
Select the Species check box for the species for which to specify the flux, 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 )

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 181

 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.

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 relation between the
concentration of a solute species in two adjoining 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.

Select Partition coefficient from the Relation list to prescribe a linear relationship
between the concentration on either side of a boundary. For a species concentration
ci, the ratio between the concentration on the upside and on the downside of the
boundary (ci,u and ci,d respectively) is then defined in terms of a partition coefficient
Ki in the manner of

182 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

 c i, u
K i = ---------
c i, d

Use the associated input field to prescribe the partition coefficient for each species.

Select User defined from the Relation list to set up a nonlinear relation between the up
and downside concentrations. For such relations f(ci)u=f(ci)d, where f(ci)u is the
expression enforced on the upside. Use the associated input fields to enter the upside
and downside expressions for each species.

The up and downside of the selected boundary is indicated with a red arrow in the
Graphics window. The arrow points from the downside into the upside. Select the
Reverse direction check box to reverse the direction of the arrow on the selected
boundary, and update the definition of the up and downside concentrations
accordingly.

This feature is only available in a limited set of add-on products. See

[Link] for more details on
availability.

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.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 183

 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

[Link] for more details on
availability.

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.

184 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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

[Link] 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.

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 TRANSPORT OF DILUTED SPECIES INTERFACE | 185

 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

[Link] 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.

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 a reaction where the kinetics is so fast that the equilibrium
condition is fulfilled at all times. The node solves for an additional degree of freedom
(the reaction rate Req) to fulfill the equilibrium condition at all times in all space
coordinates.

186 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

• A necessary requirement 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
[Link] 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). Also enter
a value or expression for the Unit activity concentration Ca0 (SI unit: mol/m3).
Selecting Equilibrium constant defines 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.

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.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 187

 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
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

[Link] 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

[Link] for more details on
availability.

188 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

Porous Electrode Coupling
Use this node to add a molar source in a domain that is coupled to one or multiple
Porous Electrode 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
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

[Link] 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.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 189

 Electrode Surface Coupling
Use this node to define a flux boundary condition based on current densities of one or
multiple Electrode 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.

Note that if you are also modeling the momentum transport and expect a
nonnegligible 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

[Link] for more details on
availability.

Porous Medium
Use this node to model the concentration of diluted species transported by a solvent
(mobile fluid phase) through interstices in a solid porous medium. In addition to
transport due to convection and diffusion, the node contains functionality to include
species evolution through adsorption and dispersion.

This feature is only available in a limited set of add-on products. See

[Link] for more details on
availability.

Species transport through a porous medium is affected both by properties of the fluid
phase, and as well as properties of the solid matrix. These properties are defined in the
Fluid and Porous Matrix subnodes respectively. The Porous Medium node supports
material properties using a Porous Material node (described in the COMSOL
Multiphysics Reference Manual), where properties are defined per phase in a similar
manner.

Add an Adsorption or a Dispersion subfeature to the Porous Medium to account for the
corresponding transport mechanism.

190 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

Fluid
Use this node to specify the mass transfer in the mobile fluid solvent filling the pores
of a porous medium. It is used as a subnode to Porous Medium.

MODEL INPUTS
The temperature model input is always available. By default, the Temperature model
input is set to Common model input, and the temperature is controlled from Default
Model Inputs under Global Definitions or by a locally defined Model Input. If a Heat
Transfer interface is included in the component, it controls the temperature Common
model input. Alternatively, the temperature field can be selected from another 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 for T.

You can also select User defined from the Temperature model input in order to manually
prescribe T.

CONVECTION
If transport by convection is active, the velocity field of the solvent needs to be
specified. 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
Use this section to specify diffusion coefficients describing the diffusion of each species
in the solvent fluid.

Use the Source list to select to pick up diffusion coefficients defined in a material or a
Chemistry interface.

Select Material, and a Fluid material to use a diffusion coefficient in a material available
in the model. User-defined property groups including a diffusion coefficient output
property are available for selection in the Fluid diffusion coefficient list.

Select Chemistry to use a diffusion coefficient from a Chemistry interface added to

model component. Diffusion coefficients are automatically defined when Calculate
transport properties is selected on the interface level of a Chemistry interface. All
defined diffusion coefficients are available for selection in the Fluid diffusion coefficient
list.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 191

 For User defined, enter a value or expression for the Fluid diffusion coefficient DF,i of
each species in the corresponding input field.

In a porous medium the diffusivity is reduced due to the fact that the solid grains
impede Brownian motion. Select an Effective diffusivity model to account for the
reduced diffusivity. The available models are Millington and Quirk model (the default),
Bruggeman model, Tortuosity model, or No correction. For Tortuosity model, enter a
value for the tortuosity τF,i (dimensionless).

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: https:/
/[Link]/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.

• For User defined, enter a value or expression for the Electric potential V. This input
option is always available.
• Select the electric potential solved by an AC/DC-based interface that has added to
the component.
• Select the electric potential defined or solved for by an Electrochemistry interface
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, select the
appropriate scalar or tensor type — Isotropic, Diagonal, Symmetric, or Full — and type
in the value or expression of the effective mobility ume,i.

Enter the Charge number zc for each species.

Porous Matrix
This node sets the porosity when modeling transport of diluted species in a Porous
Medium or a Unsaturated Porous Medium.

The default Porosity εp of the solid matrix is taken From material. The Porous Matrix
node supports the use of a Porous Material node, where the porosity is defined in the
manner of

192 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

 εp = 1 –  θs, i – θimf, i
i i

where θs,i and θimf,i are the porosities of the Solid and Immobile Fluids subnodes under
the Porous Material node.

Select From pellet bed densities to compute the porosity using the (dry bulk) Bed
density ρb and the (single phase) Pellet density ρpe. The porosity is then defined from

ρb
ε p = 1 – --------
ρ pe

For User defined, enter a value or expression for the porosity.

Dispersion
Local variations in the velocity as the fluid flows around solid particles lead to
mechanical mixing, referred to as dispersion. Use this feature to account for dispersion
in a Porous Medium or a Unsaturated Porous Medium

This subfeature is available when both the Mass transfer in porous media mass transfer
check box and the Convection check box are 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. When not selected the
same dispersion tensor DD is used for all species.

Select an option from the Dispersion tensor list — Dispersivity or User defined.

Select Dispersivity to specify the dispersion in terms of dispersivities (SI unit: m). 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.

For User defined, specify the dispersion components in terms of constants or

expressions. Select Isotropic, Diagonal, Symmetric, or Full to enable the appropriate
tensor components.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 193

 Unsaturated Porous Medium
Use this node to model the concentration of diluted species transported by a solvent
(mobile fluid phase) through interstices in a solid porous medium. In addition to
transport due to convection and diffusion, the node contains functionality to include
species evolution through adsorption and dispersion.

Use this node to model the concentration of diluted species transported by a liquid
(mobile fluid phase) in a partially filled solid porous medium. The interstices of the
porous medium contains the liquid carrier phase and gas pockets. Apart from
convection and diffusion, the node contains functionality to include species evolution
through adsorption, dispersion, and volatilization.

This feature is only available in a limited set of add-on products. See

[Link] for more details on
availability.

The properties of each phase present are defined using the Liquid, the Gas, and the
Porous Matrix subnodes respectively. The Unsaturated Porous Medium node supports
material properties using a Porous Material node (described in the COMSOL
Multiphysics Reference Manual), where properties are defined per phase in a similar
manner.

Add an Adsorption or a Dispersion subfeature to the Unsaturated Porous Medium to

account for the corresponding transport mechanism.

Liquid
Use this node to specify the mass transfer in the mobile liquid solvent present in the
pores of the Unsaturated Porous Medium.

MODEL INPUTS
The temperature model input is always available. By default, the Temperature model
input is set to Common model input, and the temperature is controlled from Default
Model Inputs under Global Definitions or by a locally defined Model Input. If a Heat
Transfer interface is included in the component, it controls the temperature Common
model input. Alternatively, the temperature field can be selected from another 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 for T.

194 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

You can also select User defined from the Temperature model input in order to manually
prescribe T.

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 θl = εps.

For Liquid volume fraction, enter a value for θl (dimensionless) between 0 and the value
of the porosity.

Select a Liquid fraction time change: Liquid fraction constant in time (the default), Time
change in liquid 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). If a Darcy’s Law interface is included in the
component, the time change in pressure head solved for can be selected.

CONVECTION
If transport by convection is active, the velocity field of the solvent needs to be
specified. 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
Use this section to specify diffusion coefficients describing the diffusion of each species
in the solvent liquid.

Use the Source list to select to pick up diffusion coefficients defined in a material or a
Chemistry interface.

Select Material, and a Liquid material to use a diffusion coefficient in a material available
in the model. User-defined property groups including a diffusion coefficient output
property are available for selection in the Liquid diffusion coefficient list.

Select Chemistry to use a diffusion coefficient from a Chemistry interface added to

model component. Diffusion coefficients are automatically defined when Calculate
transport properties is selected on the interface level of a Chemistry interface. All

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 195

 defined diffusion coefficients are available for selection in the Liquid diffusion coefficient
list.

For User defined, enter a value or expression for the Liquid diffusion coefficient DL,i of
each species in the corresponding input field.

In a porous medium the diffusivity is reduced due to the fact that the solid grains
impede Brownian motion. Select an Effective diffusivity model, liquid to account for the
reduced diffusivity in the liquid. The available models are Millington and Quirk model
(the default), Bruggeman model, Tortuosity model, or No correction. For Tortuosity
model, enter a value for the tortuosity τL,i (dimensionless).

Note that multiple species, as well as Migration in Electric fields (described below) is
only available for certain COMSOL Multiphysics add-on products. For details see:
[Link]

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.

• For User defined, enter a value or expression for the Electric potential V. This input
option is always available.
• Select the electric potential solved by an AC/DC-based interface that has added to
the component.
• Select the electric potential defined or solved for by an Electrochemistry interface
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, select the
appropriate scalar or tensor type — Isotropic, Diagonal, Symmetric, or Full — and type
in the value or expression of the effective mobility ume,i.

Enter the Charge number zc for each species.

Gas
Use this node to specify the mass transfer in the gas phase present in the pores of the
Unsaturated Porous Medium.

196 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

DIFFUSION
The settings for the diffusion of each species in the gas phase are identical to those in
the Liquid subnode.

VOLATILIZATION
Enter a value for the volatilization isotherm kG,c (dimensionless) for each species.

Adsorption
Use this node to model adsorption of the (fluid phase) solute species onto the surface
of the porous matrix. It is available as a subnode to the Porous Medium and the
Unsaturated Porous Medium nodes.

This feature is only available in a limited set of add-on products. See

[Link] for more details on
availability.

MATRIX PROPERTIES
The density of the porous media is needed when modeling adsorption to the surface
of the porous matrix. Choose to input either the Dry bulk density ρ, or the Solid phase
density ρs. The former is the density of the porous matrix including empty pores, while
the latter corresponds to the density of the pure solid phase. The density can be defined
from the domain material by selecting From material, or from a user defined expression.
When a Porous Material is used on the selection, the density will be requested from a
Solid subfeature. Several Solid features can be used to model a homogeneous mixture
of several solid components.

ADSORPTION
Select an Adsorption isotherm — Langmuir, Freundlich, Toth, BET, 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 | 197

 KL c ∂c P K L c Pmax
c P = c Pmax -------------------- , K P = -------- = ---------------------------2
1 + KL c ∂c ( 1 + KL c )

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  -------- , K P = -------- = N -----
 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 Toth:
bT c
c P = c Pmax ----------------------------------------------
N 1 ⁄ NT
( 1 + ( bT c ) T )

and

–  1 + -------
1
∂c P  N T
N
KP = -------- = c Pmax b T ( 1 + ( b T c ) T )
∂c

Enter a Toth constant bT,c (SI unit: m3/mol), a Toth exponent NT,c (dimensionless),
and an Adsorption maximum cp,max,c (SI unit: mol/kg).
• For BET (Brunauer-Emmett-Teller):
KB c0 c
c P = --------------------------------------------------------------
( c S – c )  1 + ( K B – 1 ) -----
c
 c S

and

2 2
∂c P K B c 0 c S ( ( K B – 1 )c + c S )
K P = -------- = -----------------------------------------------------------------
-
∂c 2
( c – c S ) ( c S + ( K B – 1 )c )
2

Enter a BET constant KB,c (dimensionless), a Monolayer adsorption capacity c0,c

(SI unit: mol/kg), and an Saturation concentration cS,c (SI unit: mol/m3).
• For User defined enter an Adsorption isotherm cP,c (SI unit: mol/kg):

198 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

 cP = f ( c )

For more information, see Adsorption in the theory section.

FURTHER READING
See the theory chapter in the section Mass Balance Equation for Transport of Diluted
Species in Porous Media.

Volatilization
This feature is available when the Mass transfer in 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
species dissolved in the liquid are assumed to be vaporized at the boundary, and
transported 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

[Link] 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 Unsaturated Porous
Medium domain.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 199

 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.

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 volumetric 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.

This feature 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 https://
[Link]/products/specifications/.

200 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

Out-of-Plane Flux
The out-of-plane flux node is used to prescribe a flux in an out-of-plane domain, and
it can be used to reduce a model geometry to 2D, or even 1D, when the concentration
variation is small in one or more directions. This could be the case for example when
the object to model is thin or slender. Figure 5-1shows examples of possible situations
in which this type of geometry reduction can be applied.

Jz

Jup

Jdown

Figure 5-1: Geometry reduction from 3D to 1D (top) and from 3D to 2D (bottom).

For a 1D component this node adds a single out-of-plane molar flux J0,z,i for species
i. For a 2D component two fluxes can be prescribed for each species; J0,u,i for the
upside of the domain, and J0,d,i for the downside of the domain.

The fluxes are added as a source contribution to the right-hand side of the transport
equation. For example, in 2D components with diffusion, convection and out-of-plane
flux present, mass transfer of species i is defined by the mass conservation equation

∂c i
------- + ∇ ⋅ J i + u ⋅ ∇c i = R i + S , (5-1)
∂t opf, i

where Sopf,i is the out-of-plane source for species i

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 201

 J 0, i J 0, u, i + J 0, d, i
S opf, i = ---------- = -------------------------------------- .
dz dz

For external convection on the upside and the downside of the domain, the
out-of-plane flux is

J 0, i = k c, u, i ( c b, u, i – c i ) + k c, d, i ( c b, d, i – c i )

where kc is a mass transfer coefficient and cb is the bulk concentration, the typical
concentration far into the surrounding exterior domain. The prescribed flux, J0, can
include any arbitrary user-specified expressions. It can be a constant or a function of a
dependent variable or independent variables.

UPSIDE INWARD FLUX

For 1D components, enter the cross-sectional perimeter Pc to get the out-of-plane flux

J 0, i = P c J 0, z, i .

The default value of Pc is the circumference. Either keep the default value, for a circular
cross-section shape, or edit the value to get a user-defined shape of the out-of-plane
cross-section.

The available flux type options are General inward flux and External convection. Select
the Species check box for the species for which to specify the flux, 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.

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.

DOWNSIDE INWARD FLUX

The available options are General inward flux and External convection. The settings are
the same as for the Upside Inward Flux section.

202 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

FURTHER READING
For an example of using the Out-of-Plane Flux node, see this application example:

Mass Transfer from a Thin Domain: Application Library path

Chemical_Reaction_Engineering_Module/Tutorials/thin_domain

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

[Link] 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.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 203

 For User defined, enter values or expressions for the velocity components in the table
shown.

The settings for the Diffusion is the similar to the settings for the diffusion
coefficients in the Fluid node. The Dispersion settings are identical to the
ones in the Dispersion node.

204 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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, and so on) 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 INPUT
This section sets the Temperature, Pressure and Electrode potential (only available with
a Battery Design Module, Corrosion Module, Electrochemistry Module,
Electrodeposition Module, or Fuel Cell & Electrolyzer Module license) to be used by
the current interface. Toggle the Enable electrode reactions check box to enable the
Electrode Potential input in the Model Input section, as well as the Electrode Reaction
and Electrode Reaction Group features. Use the lists to select a temperature, pressure

THE CHEMISTRY INTERFACE | 205

 or electrode potential defined and announced by another interface in the model. For
example, when a heat transfer interface is also included, the temperature solved for is
available in the Temperature list.

For Temperature or Pressure, you can also select Common model input to use a globally
available common model input. In all three cases, select User defined to manually define
the variable in question.

MIXTURE PROPERTIES

Type
Use this setting to define specify what kind of mixture assumption is used. For Diluted
Species the mixture is composed of low concentration solutes present in a solvent. For
Concentrated Species a mixture where no single species is considered to be in excess is
assumed.

Select Diluted species from the Type list to use the concentration variables from a
Transport of Diluted Species interface in the Species Matching section. The same
setting should be used for any other interface solving for molar concentrations using a
diluted species assumption. Select Concentrated species from the Type list to use the
mass fractions from a Transport of Concentrated Species interface.

Thermodynamics
All property parameters and property functions required by the interface can be
automatically created by coupling to a system added to the Thermodynamics node. To
do so, click the Thermodynamics check box and select an existing Thermodynamic
System.

The Thermodynamics check box is enabled when the Thermodynamics node, including
one or more systems, is available under Global Definitions. Also, the Chemistry interface
needs to include at least one species.

Phase
Use the Phase list to specify the state of aggregation of the mixture.

SPECIES MATCHING
This section is used to match species solved for in space dependent physics interfaces
to the species defined in Chemistry. By doing so the variables for the reaction kinetics
and the mixture properties defined by Chemistry can be applied to study chemically
reacting or composition dependent systems.

206 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

Species solved for
Use this list to populate the inputs in the Bulk species table with dependent variables
from a certain mass transfer interface. The Species solved for list contains all present
interfaces of the Type selected in the Mixture Properties section. For example, when the
Type is Diluted species, all Transport of Diluted Species interfaces or variants thereof,
such as Transport of Diluted Species in Porous Media interface, are available in the list.

Bulk Species
Use the Bulk species table to specify the concentrations to be used as arguments in
reaction kinetics variables, for example the reaction rate. Reaction kinetics variables are
generated by the species features (Species and Species Group) and by the reaction
features (Reaction, Electrode Reaction, Reversible Reaction Group, Electrode
Reaction Group, and Equilibrium Reaction Group).

The bulk species concentrations are also used in the mixture properties, both for
transport properties like the density and viscosity, and thermodynamic properties like
the enthalpy or heat capacity.

When a mass transfer interface has been selected in the Species solved for list, use the
Molar concentration column to select one of the dependent variables in the selected
interface to the corresponding Species in Chemistry. When using a concentrated
species interface (defined by the Type list in the Mixture Properties section), instead
use the Mass fraction column to select a dependent variable for each species in
Chemistry.

The Molar concentration and Mass fraction columns also includes a User defined option,
in which case a constant, parameter, or variable expression can be entered in the Value
column.

Thermodynamics Coupling
When the Thermodynamics is enabled, the species in the Chemistry interface can be
coupled to the species in the Thermodynamic System. This is needed to ensure that
arguments for the thermodynamic functions are correctly defined. Use the drop-down
lists in the From Thermodynamics column to match each species in the Chemistry to a
species in the coupled thermodynamic system. For each thermodynamics-coupled
species, the required property parameters and functions are added under the
corresponding thermodynamic system. When all species are matched, the Chemistry is
considered fully coupled and functions representing mixture properties, such as the
density, are also added automatically under the same thermodynamic system.

THE CHEMISTRY INTERFACE | 207

 Surface Species
It is available when there is any surface species (with “(ads)” as suffix).

Specify the concentration of surface species in the table in this section. In addition, if
a surface species is present at the same time as an Electrode Reaction, the Density of
sites input field becomes visible. The Density of sites input value will be used as the
default reference concentration for surface species reacting in an Electrode Reaction.

The species present in this section will not be used to define mixture properties.

Solid Species
It is available when there is any solid species (with “(s)” as suffix).

Specify the concentration of solid species in the table in this section.

The species present in this section will not be used to define mixture properties.

Aqueous Species
It is available when there is any aqueous species (with “(aq)” as suffix).

Specify the concentration of solid species in the table in this section.

The species present in this section will not be used to define mixture properties.

Equilibrium Reaction Rate Table

This table is only available when equilibrium reactions are present in the interface. Use
the Reaction rate column to specify the rate for each equilibrium reaction. By doing so
the postprocessing variable for the total reaction rate for each species, of form
chem.Rsum_species, will be updated correctly. For a mass transport interface, say
Transport of Diluted Species, the reaction rate needed for an equilibrium reaction is
typically a dependent variable. In that case, the name of the variable can be found in
the Shape Function section of the Equation View of the node.

When the Chemistry interface is created using from the Generate Space-Dependent
Model the table is automatically set up in accordance with the added equilibrium
reaction nodes.

CALCULATE TRANSPORT PROPERTIES

Select the Calculate mixture properties check box (selected as default) to calculate
mixture properties that can be picked up in the space-dependent model interfaces. The
properties that can be calculated are shown beneath the check box. Consider also if the
built-in Automatic expressions fit the model or if User defined expressions are more

208 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

suitable. In general, the Chemistry interface calculates properties in the same way as
the Reaction Engineering interface.

Transport Properties

ACTIVITY
This section is available when the Thermodynamics check box is cleared.

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.

CHEMKIN IMPORT FOR SPECIES PROPERTIES

It is available when the Thermodynamics check box is cleared.

This section enables CHEMKIN® import to simulate complex chemical reactions in

gas phase.

Two types of CHEMKIN input files can be imported here: Thermo and Transport, for
thermodynamic properties and transport properties, respectively. Properties for either
volumetric or surface species are supported. Click Browse to locate the CHEMKIN file
to be imported, then click Import. For Thermo, the imported data is directly entered in
the NASA format fields in the Species node’s Thermodynamic Expressions section; for
Transport, the imported data is entered in its Transport Expressions section.

THE CHEMISTRY INTERFACE | 209

 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
• Electrode Reaction • Species Thermodynamics1
• Electrode Reaction Group
• Reversible Reaction Group
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.

Balance ( )
If all species are written using their chemical formula, the stoichiometric coefficients
can automatically be calculated, if the problem is well posed, by clicking the Balance
button to the right of the Reaction Formula section title. This turns, for example, the
formula “H2+O2=>H2O” into “2H2+O2=>2H2O”.

Examples of problems that are not well posed are, for example,
“C+H2=>CH4+C2H6”, from which any ratio of CH4/C2H6 could be obtained, and
“H2=>O2”, where not all elements are present on both sides.

210 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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 reaction i contributes
to the change in species i as follows:

Ri =  νij rj (5-2)
j

where νij is the stoichiometric coefficient.

• If it is an Equilibrium reaction, 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.

When Mass action law is selected (default), the rate expression is automatically derived
from the stoichiometric coefficients in the reaction formula:

• For an Irreversible reaction type, the reaction rate becomes:

– ν ij
∏
f
rj = kj ci (5-3)
i ∈ react

• For a Reversible reaction type, the expression instead becomes:

– ν ij ν
∏ ∏
f r
rj = kj ci – kj c i ij (5-4)
i ∈ react i ∈ prod

The deduced overall reaction order is shown in text below the respective equation in
the Reaction Rate section.

THE CHEMISTRY INTERFACE | 211

 Arbitrary Rate Expression
If the reaction order differs from the stoichiometric coefficients, or if an arbitrary rate
expressions is applicable, change Reaction Rate to User defined. An expression field r
appears with the default expression being that from the mass action law. Below this
there are fields to set the reaction order. For a reversible reaction the reverse reaction
order may be specified in addition to the forward one. The unit of the rate constant k
(or frequency factor A in the case of Arrhenius behavior), is derived from the reaction
order, in SI units: (m3/mol)α − 1/s, where α equals the order with respect to
volumetric species. When surface species are present — identified by their “(ads)”
suffix — the unit is instead given by m3α+2β − 2/molα+β−1/s, where β is the order with
respect to surface species.

Consider for example the reaction:

2 S 2 O 42 – + H 2 O  S 2 O 32 – + 2 HSO 3–

The automatically deduced reaction order is three, however, in the case that water is
the solvent, the order should probably be two. This is specified as follows:

Change to User defined

Adjust rate expression

Specify reaction order

Note effect on unit

Figure 5-2: The reaction order can be manually specified for a user defined reaction rate.

212 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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 5-3).

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.

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 ) )

r
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 (unit depends on

reaction order)
• Forward temperature exponent nfand Reverse temperature exponent nr
• Forward activation energy Efand Reverse activation energy Er (SI unit: J/mol)

THE CHEMISTRY INTERFACE | 213

 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:

ν
∏ c i ij
i ∈ prod
K eqj = ---------------------------
–ν
∏ c i ij
i ∈ react

Select User defined from the Equilibrium expression list to instead enter a manually
defined equilibrium expression.

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.

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 nonideal 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 contains information about thermodynamic properties that relate to a
selected reaction. Several Automatic definitions are available here.

214 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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 (5-5)
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 (5-6)
i ∈ prod i ∈ react

In Equation 5-5 and Equation 5-6, hi and si are the species’ molar enthalpy and molar
entropy, respectively.

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, νij, are defined as being negative for reactants and
positive for products. Using Equation 5-5 and Equation 5-6 to equate the Gibbs free
energy of reaction enables the equilibrium constant to be expressed according to
Equation 5-5.

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.

THE CHEMISTRY INTERFACE | 215

 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 [Link] latter is only
available when a diluted solution is assumed. That is when Type is set to Diluted Species
in the Mixture Properties section (in the interface level).

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.

The default value for the Molar mass, M, and the ionic Charge, z, of the species is
automatically defined from the species name by assuming that it corresponds to its
chemical formula. Provided that the formula contains elements from the periodic
table, the species molar mass is computed from the mass of occurring individual
elements1. When the species name contains parts not in the periodic table, for example
when a descriptive name such as water is used, the molar mass is set to 0.0 kg/mol
and the charge to zero. In this case, the molar mass needs to be defined in order to
achieve mass balanced reactions and correct definitions of mass basis properties. The
species charge is also deduced from the species name. Creating a H+ species, the charge
1. Values are averages of upper and lower bounds for each atom as published by CIAAW. Source: CIAAW.
Atomic weights of the elements 2019. Available online at [Link].

216 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

will be set to one. When needed, both the Molar mass and the Charge can be edited in
the corresponding text field.

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, nonreactive).

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 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 input field. This input field is only shown if activity instead of
concentration has been chosen in the interface, that is, the Use activity check box is
selected on the Chemistry interface Settings window

Click to select the Constant 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.

Choose the User defined alternative to specify Cp, h, and s directly.

Electrode Reaction
To add an Electrode Reaction node ( ) either right-click the Chemistry node or on
the Chemistry toolbar click Electrode Reaction.

THE CHEMISTRY INTERFACE | 217

 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.

This node is available with a Battery Design Module, Corrosion Module,

Electrochemistry, Module, Electrodeposition Module, or Fuel Cell & Electrolyzer
Module license.

REACTION FORMULA

Formula
Enter an electrode reaction Formula, as a reduction reaction. Use the single letter “e”
to symbolize an electron. The delimiter between reactants and products has to be
written as “<=>” (without quotation marks). The phase of the species, that is (aq) for
aqueous dilute ions, (s) for solids, and (g) for gases can be indicated in the name. The
phase is used to select an automatic reference state (see Reference Concentrations) for
computing the equilibrium potential using the Nernst equation. 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.

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.

Nernst Equation
After providing the reference electrode potential, the equilibrium potential is
calculated using the Nernst equation. The concentrations entered in the Species
Matching section of the Chemistry interface will be used to calculate the equilibrium
potential. The reference concentrations, defined in the Reference Concentrations
section, will be used to compute the activities in the reaction quotient expression, Qr.

Automatic
This option is only available if the Calculate Transport Properties option is checked.

The Species enthalpies and entropies are used to calculate the equilibrium potential of
the electrode reaction at the temperature and composition of the system.

If only species enthalpies and entropies at standard state are available, use the Nernst
Equation option instead.

218 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

REFERENCE CONCENTRATIONS
The reference concentrations for the species in the reaction can be changed here.

Automatic
The phase indicated when first naming a species will be used to select a suitable
reference concentration. The species must indicate the phase in the name when the
species is first created.

For aqueous dilute species, denoted by (aq) in their names, the activity is calculated as
their concentration divided by 1 M. For gaseous species, denoted by (g) in their
names, the activity is calculated as their concentration divided by the standard
reference pressure of 1 atm, converted into concentration using the ideal gas law. For
solid species, denoted by (s) in their names, the reference concentration 1. For surface
species, denoted by (ads) in their names, the reference surface concentration will be set
to the site density configured in the Species Matching section. Any species not
containing a phase in their name, will use a reference state depending on the phase
selected under Mixture Properties. If the phase is Gas, the gaseous species reference
concentration described above will be used, while if the phase is Liquid, the aqueous
species 1 M reference concentration will be used.

User Defined
The reference concentrations for each type of species can be set manually, for aqueous,
gaseous, solid, surface and any other species, respectively.

ELECTRODE KINETICS
See the Electrode Reaction node in Shared Physics Features in the Current
Distribution Interfaces for a general description of the Electrode Kinetics section.

Electrode reactions in the Chemistry interface support User-defined, Butler-Volmer and

Linearized Butler-Volmer kinetics. For the latter two options, User-defined exchange
current densities and exchange current densities according to the Mass Action Law are
supported.

If the equilibrium potential is calculated using Nernst Equation, the exponents in the
local current density expression are evaluated using the reference overpotential. If
instead the equilibrium potential is calculated using the Automatic option, the
exponents are evaluated using the overpotential.

THE CHEMISTRY INTERFACE | 219

 HEAT OF REACTION
See the Electrode Reaction node in Shared Physics Features in the Current
Distribution Interfaces for a general description of the Heat of Reaction section.
Electrode Reactions in Chemistry do not support the Temperature Derivative option.

By choosing Automatic, the Thermoneutral voltage parameter, Etherm (SI unit: V), will
be calculated according to

Δr H
E therm = – ----------- (5-7)
nF

using the Species enthalpies.

• Electrode Reactions Theory

• Electrode Kinetics Expressions

Electrode Reaction Group

To add an Electrode Reaction Group node ( ) either right-click the Chemistry node or
on the Chemistry toolbar click Electrode Reaction Group.

An Electrode Reaction Group is typically used to represents all electrode reactions

occurring on one electrode.

Multiple Electrode Reaction nodes may be added to the Electrode Reaction Group.
Variables for the sum of all electrode reactions in one group can be used as input in
Electrode Reaction features in current distribution interfaces.

This node is available with a Battery Design Module, Corrosion Module,

Electrochemistry Module, Electrodeposition Module, or Fuel Cell & Electrolyzer
Module license.

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.

220 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

For the case when reaction kinetics data are entered manually into the Reaction table
and temperature dependent reaction kinetics apply, 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
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 or include a header.
• 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.

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

THE CHEMISTRY INTERFACE | 221

 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, 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 equilibrium reactions in the 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 or include a header.
• 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

222 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

 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.

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.

This node is automatically added when either the Reversible Reaction Group or the
Equilibrium Reaction Group is used.

For the case of temperature dependent reaction kinetics, 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, 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 nonideality in the fluid mixture is accounted for; when the Use activity check box
is selected in the Activity section.

THE CHEMISTRY INTERFACE | 223

 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
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.

224 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

The Nernst–Planck-Poisson
Equations 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.

THE NERNST–PLANCK-POISSON EQUATIONS INTERFACE | 225

 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

Electrodeposition_Module/Tutorials/diffuse_double_layer

226 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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, isotachophoresis, 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.

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.

DOMAIN SELECTION
If any part of the model geometry should not partake in the mass transfer model,
remove that part from the selection list.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 227

 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.

CONSISTENT STABILIZATION
To display this sections, click the Show More Options button ( ) and select
Stabilization in the Show More Options dialog box.

• 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

228 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

 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 More Options button ( ) and select Stabilization
in the Show More Options dialog box. 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 More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box. 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
To display all settings available in this section, click the Show More Options button ( )
and select Advanced Physics Options in the Show More Options dialog box.

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.

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.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 229

 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 [Link], 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 2-4 for
links to common sections and Table 2-5 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.

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

230 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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 nodes are dissociation species and may
define an arbitrary number of dissociation steps. Each dissociation step is defined by
its 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
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.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 231

 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 (about 96,485 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.

IONIC STRENGTH CONTRIBUTION

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

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.

232 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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

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 2-4 for links
to common sections and Table 2-5 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 | 233

 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.

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.

234 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

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 .

THE ELECTROPHORETIC TRANSPORT INTERFACE | 235

 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 More Options button ( ) and select
Advanced Physics Options in the Show More Options dialog box.

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.

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, which
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.

236 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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 More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

Species Source
To make this node available, click the Show More Options button ( ) and select
Advanced Physics Options in the Show More Options dialog box.

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.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 237

 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.

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.

238 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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
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 are the
dominating transport mechanisms across outflow boundaries, and therefore that
diffusive transport can be ignored; that is:

n ⋅ ( – D ∇c ) = 0

THE ELECTROPHORETIC TRANSPORT INTERFACE | 239

 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.

240 | CHAPTER 5: 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 More Options button ( )
and select Advanced Physics Options in the Show More Options dialog box.

CONSISTENT AND INCONSISTENT STABILIZATION

To display these sections, click the Show More Options button ( ) and select
Stabilization in the Show More Options dialog box.

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
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 [Link] 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 | 241

 • 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 2-4 for links
to common sections and Table 2-5 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 Full 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.

242 | CHAPTER 5: 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,
2
cb2, cb3, … (SI unit: mol/m ) 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 | 243

 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 More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

244 | CHAPTER 5: 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 on the composition, and a different physics interface is recommended. See The
Transport of Concentrated Species Interface in the Chemical Reaction Engineering
Module User’s Guide 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:

• Adding Transport Through • Mass Balance Equation

Migration • Mass Sources for Species Transport
• Convective Term Formulation • Solving a Diffusion Equation Only
• Crosswind Diffusion • Supporting Electrolytes
• Danckwerts Inflow Boundary • References
Condition
• Equilibrium Reaction Theory

Note: Some features explained in this section require certain add-on modules. For
details see [Link]

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 245

 The section also includes the theory for The Transport of Diluted Species in Porous
Media Interface:

• Adsorption • Mass Balance Equation for

• Convection in Porous Media Transport of Diluted Species in
Porous Media
• Diffusion in Porous Media
• Mass Transport in Fractures
• Dispersion
• Reactions

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
------- + ∇ ⋅ J i + u ⋅ ∇c i = R i (5-8)
∂t

Equation 5-8 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 mass averaged velocity vector (SI unit: m/s)
• Ji is the mass flux diffusive flux vector (SI unit: mol/(m2·s))

The mass flux relative to the mass averaged velocity, Ji (SI unit: mol/(m2·s)), is
associated with the mass balance equation above and used in boundary conditions and
flux computations. The Transport of Diluted Species interface always includes mass
transport due to molecular diffusion. In this case the mass flux Ji defines the diffusive
flux vector

J i = – D ∇c i (5-9)

An input field for the diffusion coefficient is available.

246 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

When Migration in Electric Fields is activated, the migration term is also added to
the diffusive flux vector as shown in the section Adding Transport Through Migration.

The third term on the left side of Equation 5-8 describes the convective transport due
to a velocity field u. This field can be expressed analytically or obtained from coupling
the physics interface to one that solves for fluid flow, such as Laminar Flow. Note that
all fluid flow interfaces solve for the mass averaged velocity.

On the right-hand side of the mass balance equation (Equation 5-8), 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
interface — the Reaction node for example, which includes an input field for specifying
a reaction expression 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.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 247

 Defining the stoichiometric coefficients positive for products and negative for
reactants, the above equilibrium condition can also be written:

νi
K eq = ∏ ai
i

The Equilibrium Reaction node solves for a reaction rate so that the equilibrium
condition is always fulfilled in the domain. It is available for the Chemical Reaction
Engineering Module; Battery Design Module; Corrosion Module; Electrochemistry
Module; Electrodeposition Module; and Fuel Cell & Electrolyzer Module.

γc,i is set to unity when the Equilibrium constant is selected on the

Settings window. For nonunity 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.

248 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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,
solving for a stationary problem with all nonequilibrium 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 (depending on the
modules licensed, a check box to activate migration is available) and implements the
mass balance equation in Equation 5-8.

There are two ways to present a mass balance where chemical species transport occurs
through diffusion and convection. These are the nonconservative and conservative
formulations of the convective term:

∂c
nonconservative: ----- + u ⋅ ∇c = ∇ ⋅ J i + R (5-10)
∂t

∂c
conservative: ----- + ∇ ⋅ ( cu ) = ∇ ⋅ J i + R (5-11)
∂t

and each is treated slightly differently by the solver algorithms. In these equations
Ji (SI unit: mol/(m2·s)) is the diffusive flux vector, 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 nonconservative formulation above. This is in fact the default
formulation in this physics interface. To switch between the two formulations, click the
Show button ( ) and select Advanced Physics Options.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 249

 Solving a Diffusion Equation Only
Remove the convection term from Equation 5-10 and Equation 5-11 by clearing the
Convection check box in the Transport Mechanisms section for The Transport of
Diluted Species Interface. The equation then becomes

∂----c-
= ∇ ⋅ Ji + R
∂t

Mass Sources for Species Transport

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
[Link]

There are two types of mass sources in the Transport of Diluted Species interface: point
sources and line sources.

POINT SOURCE
·
A point source is theoretically formed by assuming a mass injection/ejection, Q c (SI
unit: mol/(m3·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 (5-12)
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 5-12, 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.

250 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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 5-12 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
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
unit: mol/(m3·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 (5-13)
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.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 251

 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
[Link]

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 (5-14)
∂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) is its ionic mobility

In this case the diffusive flux vector is

J i = – D i ∇c i – z i u m, i Fc i ∇V

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 Electrostatics interface. Sometimes it is assumed to be a supporting electrolyte
present, which simplifies the transport equations. In that case, the modeled charged
species concentration is very low compared to other ions dissolved in the solution.
Thus, the species concentration does not influence the solution’s conductivity and the
net charge within the fluid.

252 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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) is the
temperature.

Note: In the Nernst–Planck Equations interface, the ionic species contribute to the
charge transfer in the solution. It 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

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 253

 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:

 – z j u m , j F c j ∇φ
2
i = F (5-15)
j

Equation 5-15 is simply Ohm’s law for ionic current transport and can be simplified to

i = – κ ∇φ (5-16)

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 5-16, yields:

∇ ⋅ ( – κ ∇φ ) = 0 (5-17)

Equation 5-17 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 a 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 in the COMSOL
Multiphysics Reference Manual. The method reduces over- and undershoots to a
minimum, even for anisotropic meshes.

254 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

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
underresolved 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 upstream concentrations and the fluid velocity at the
boundary. In chemical engineering, this type of flux boundary condition is also known
as a Danckwerts condition.

Use the Danckwerts condition to specify inlet conditions for domains where high
reaction rates are anticipated in the vicinity to the inlet (Ref. 2).

Given an upstream concentration ci,0, the Danckwerts inflow boundary condition

prescribed the total flux as

n ⋅ ( J i + uc i ) = n ⋅ ( uc i, 0 ) (5-18)

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 255

 Mass Balance Equation for Transport of Diluted Species in Porous
Media

VARIABLY SATURATED POROUS MEDIA

The following equations for the molar 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:

∂ ( θ c ) + ∂ ( ρc ) + ∂ (θ c ) + u ⋅ ∇c =
P, i ∂ t g G, i
∂t l i ∂t i
(5-19)
∇ ⋅ [ ( D D , i + D e , i ) ∇c i ] + R i + S
i

On the left-hand side of Equation 5-19, 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 5-19 ci denotes the concentration of species i in the liquid (SI unit: mol/
m3), cP, i the amount adsorbed to 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 θl; the dry bulk density, ρ = (1 − εs)ρs, and the
solid phase density ρs.

For saturated porous media, the liquid volume fraction θl is equal to the porosity εp,
but for unsaturated porous media, they are related by the saturation s as θl = εps. The
resulting gas volume fraction in the case of an unsaturated porous medium is

θ g = ε p – θ l = ( 1 – s )ε p

On the right-hand side of Equation 5-19, the first term introduces the spreading of
species due to mechanical mixing resulting from the porous media (dispersion), as well
as from diffusion and volatilization to the gas phase. The dispersion 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 5-19 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.

256 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

Adsorption
The time evolution of the adsorption, the solute transport to or from the solid phase,
is defined by assuming that the amount of solute adsorbed to the solid, cP,i, is a
function of the concentration in the fluid ci. This implies that the solute concentration
in the liquid and solid phase are in instant equilibrium. The adsorption term can be
expanded to give

∂c P, i ∂c i ∂ε p ∂c i ∂ε p
∂ ρc = ρK P,i – c P, i ρ s (5-20)
( P, i ) = ρ – c P, i ρ s ∂ t ∂t
∂t ∂ ci ∂ t ∂t

where KP,i = ∂cP,i/∂ci is the adsorption isotherm.

Volatilization
Volatilization is the process where a solute species in the liquid is transported to the
gas phase due to vaporization. Assuming that the amount of solute in the gas phase,
cG,i, is a linear function of the liquid phase concentration, the volatilization term is
defined as

∂c G, i ∂c i ∂θ g ∂c i ∂θ g
∂ = θ g k G, i + k G, i c i (5-21)
θ g c G, i = θ g + k G, i c i ∂ t ∂t
∂t ∂ c i ∂ t ∂ t

where kG,i = ∂cG,i/∂ci is the linear volatilization.

SATURATED POROUS MEDIA

In the case of transport in a saturated porous medium, θl = εp, and the governing
equations are

∂ ε
( c ) + ∂ ( ρc P, i ) + u ⋅ ∇c i = ∇ ⋅ [ ( D D, i + D e, i ) ∇c i ] + R i + S i (5-22)
∂t p i ∂t

Convection in Porous Media

Convection (also called advection) 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

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 257

 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 = ---- Unsaturated
θl

where εp is the porosity and θl = sεp the liquid volume fraction, and s the saturation,
a dimensionless number between 0 and 1.

Figure 5-3: 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 5-19 is written as:

258 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

 ∂ ( θ c ) + ∂ ( ρc ) + ∂ (θ c ) + ∇ ⋅ uc =
P, i ∂ t g G, i
∂t l i ∂t i
(5-23)
∇ ⋅ [ ( 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 nonconservative formulation described in Equation 5-19.

When using the nonconservative formulation, which is the default, the fluid is assumed
incompressible and divergence free: ∇ ⋅ u = 0. The nonconservative 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 Nonconservative form (the default) or Conservative form. The
conservative formulation should be used for compressible flow.

Diffusion in Porous Media

The effective diffusion in porous media, De, depends on the structure of the porous
material and the phases involved. Dependent on whether the transport of diluted
species occurs in free flow, saturated or unsaturated porous media, the effective
diffusivity is defined as:

De = DF Free Flow
εp
D e = ----- D L Saturated Porous Media
τL
θl
D e = ----- D L Unsaturated Porous Media
τL
θl θg
D e = ----- D L + ------ k G D G Unsaturated with Volatilization
τL τG

Here DF, DL, and DG are the single-phase diffusion coefficients for the species diluted
in a fluid, a pure liquid, and a gas phase, respectively (SI unit: m2/s), and τF, 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

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 259

 compute the tortuosity factors in partially saturated porous media according to the
Millington and Quirk model (Ref. 12):

–7 ⁄ 3 2 –7 ⁄ 3 2
τL = θl εp , τG = θg εp

and Bruggeman model

–5 ⁄ 2 2 –5 ⁄ 2 2
τL = θl εp , τG = θg εp

For saturated porous media θl = εp. The fluid tortuosity for the Millington and Quirk
model is

–1 ⁄ 3
τL = εp

and for the Bruggeman model the tortuosity is defined as

–1 ⁄ 2
τL = εp

User defined expressions for the tortuosity factor can also be applied.

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 a fluid 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.

260 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

Figure 5-4: Spreading of fluid around solid particles in a porous medium.

The dispersion 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.

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:

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 261

 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 (5-24)
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 5-24 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
Adsorption feature includes four predefined and one user defined relationships to
predict the solid concentrations, cPi from the concentration in the liquid phase, ci:

262 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

 KL c
c P = c Pmax -------------------- Langmuir
1 + KL c
c N
c P = K F  -------- Freundlich
 c ref
bT c (5-25)
c P = c Pmax ---------------------------------------------- Toth
N 1 ⁄ NT
( 1 + ( bT c ) T )
KB c0 c
c P = -------------------------------------------------------------- BET
( c S – c )  1 + ( K B – 1 ) -----
c
 c S

The above equations contains the following parameters:

• Freundlich: Freundlich constant KF (SI unit:·mol/kg), Freundlich exponent NF

(dimensionless), and reference concentration cref (SI unit: mol/m3).
• Langmuir: Langmuir constant KL (SI unit: m3/mol), and adsorption maximum
cPmax (SI unit: mol/kg).
• Toth: Toth constant bT (SI unit: m3/mol), Toth exponent NT (dimensionless), and
adsorption maximum cPmax (SI unit: mol/kg).
• BET (Braunauer-Emmett-Teller): BET constant KB (dimensionless), and a
monolayer adsorption capacity c0 (SI unit: mol/kg) and a Saturation concentration,
cS(SI unit: mol/m3).

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.

Using a Species Source feature, arbitrary expressions can be entered to define, for
example, nonequilibrium 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.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 263

 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
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.

The following expressions define some common types of reactions:

ln 2
R Li = – θ --------- c i Radioactive decay — liquid
λ Li
ln 2 ∂c Pi
R Pi = – ρ b ---------  ---------- c i Radioactive decay — solid
λ Pi ∂c i
∂c Gi
R Gi = – --------- a v  ----------- c i Radioactive decay — gas
ln 2
λ Gi  ∂c 
R Lk = θζ Li c i Creation from parent c Li — liquid
∂c Pi
R Pk = ρ b ζ Pi  ---------- c i Creation from sorbed parent c Pi — solid
∂c i
∂c Gi
R Gk = – ζa v  ----------- c i Reaction — gas
∂c

where λ is the chemical half life, ζ is a reaction rate, and the subscripts L, P, and G
denote liquid, solid, and gas phases, respectively. In the equations, the reactions either
depend on liquid concentration ci or solid phase concentrations cPi obtained using the
sorption derivative with ci or gas phase concentration cGi depending on the gas volume
fraction, the volatilization, and the liquid concentration.

Reaction rates can vary with results from other equations in your model, such as
temperature. For example, enter the Arrhenius rate law given in Ref. 13:

Ea ( T – TR )
ζ T = ζ R exp ------------------------------ (5-26)
R u TT R

264 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

In Equation 5-26, T denotes the current absolute temperature, TR denotes the
reference absolute temperature, Ea is the activation energy, and Ru is the universal gas
constant.

Mass Transport in Fractures

When thin fractures occur in porous media, fluid flow tends to move faster along the
fracture than in the surrounding media. The transport of chemical species therefore
also occur also faster in the direction of the fractures.

The fluid flow in a fracture can be modeled using Darcy’s law formulated in a thin
sheet of porous medium (a fracture):

κ
u = --- ∇ t p
μ

Here u is the tangential Darcy velocity, κ is the fracture permeability, μ the fluid’s
dynamic viscosity, and ∇tp is the tangential gradient of the fluid pressure.

The equation to solve for mass transport of species ci in a thin fracture, embedded in
a porous media, is derived from Equation 5-19. The resulting equation is:

∂ρ b c P, i ∂ε p c i
d fr  ------------------ + ------------- + ∇ t ⋅ ( D e, i ∇ t c i ) + u ⋅ ∇ t c i = d fr R i + d fr S i + n 0 (5-27)
∂t ∂t

Here dfr is the fracture thickness, cP, i the amount of species adsorbed to (or desorbed
from) the porous matrix (moles per unit dry weight of the solid), εp is the fracture
porosity, and De is the effective diffusivity. The first two terms on the right hand side
represent source terms from reactions, and n0 corresponds to out-of plane flux from
the adjacent porous domain.

In order to arrive at the tangential differential equation, the gradient is split into the
contributions normal and tangential to the fracture:

∇c i = ∇ n c i + ∇ t c i

The normal gradient is defined in the direction normal to the boundary representing
the fracture and the tangential gradient is defined along the boundary. Assuming that
the variations in the normal (thin) direction of the fracture are negligible compared to
those in the tangential direction, the gradient is simplified as:

∇c i = ∇ t c i

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 265

 Using The Transport of Diluted Species in Fractures Interface, the transport along
fracture boundaries alone is solved for. In this case the transport in the surrounding
porous media neglected and the out-of plane flux n0 vanishes.

See Fracture for more information about the boundary feature solving
Equation 5-27. See for more information about the physics interface
solving the equation on boundaries only.

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.

266 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

14. R.B. Bird, W.E. Stewart, and E.N. Lightfoot, Transport Phenomena, 2nd ed.,
John Wiley & Sons, Inc., 2007.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 267

 Theory for the Electrophoretic
Transport 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 (5-28)

where Di (SI unit: 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 (5-29)
i

where the summation is made over all species in the electrolyte.

The governing equation for the electrolyte potential is

∇ ⋅ il = Ql (5-30)

where Ql (SI unit: 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

268 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

 N+2

 zi ci = 0 (5-31)
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 (5-32)

This reaction is fast, following the equilibrium relation

2 –6
c H + c OH - = K w × 1 mol dm (5-33)

– 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 (5-34)
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 (5-35)
2 4

and

2
Σ Σ 2 –6
c OH - = --- + ------ + K w × 1 mol dm (5-36)
2 4

where

Σ =  zi ci (5-37)
i=1

MASS BALANCE EQUATIONS FOR DISSOCIATION SPECIES

Assume a set of species Si describing k dissociation steps from

THEORY FOR THE ELECTROPHORETIC TRANSPORT INTERFACE | 269

 + z +k–1
z +k z +k–1 + [ H ] [ S k0– 1 ]
S k0 ↔ S k0– 1 +H K a, 1 = ----------------------------------------
z0 + k
(5-38)
[ Sk ]

to

+ z
z +1 z + [ H ] [ S 00 ]
S k0 ↔ S 00 + H K a, k = -------------------------
z +1
- (5-39)
[ 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
(5-40)

∏ 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
(5-41)

if l>m.

Setting m=i and denoting the flux of species i by Ni using equation Equation 5-28,
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 (5-42)
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

270 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

 k k
δc i
 ------ 
 -
 δt + ∇ ⋅ N i =  Ri (5-43)
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 (5-44)

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 ) (5-45)

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 = – c H+ + (5-46)
d cH+

And from this one can derive the average squared charge according to

2 d ν z2 d z z2
z = – cH+ + = – cH+ + (5-47)
d c H+ d cH+

DIFFUSIVITY-MOBILITY RELATIONS
The Stokes radius r of a molecule is related to the diffusivity according to

kT
r = --------------- (5-48)
6πμD

THEORY FOR THE ELECTROPHORETIC TRANSPORT INTERFACE | 271

 where is the μ (SI unit: 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 = -------- (5-49)
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 = ------------------------------------ = ------------------------------ (5-50)
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 = ----------------- (5-51)
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 + (5-52)
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.

272 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

THEORY FOR THE ELECTROPHORETIC TRANSPORT INTERFACE | 273

 Theory for the Surface Reactions
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 (5-53)
∂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).

274 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

Writing the density of sites of the surface as Γs (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:

THEORY FOR THE SURFACE REACTIONS INTERFACE | 275

 R b, tot =  R b, k
k

r b, tot =  r b, k
k

v b, tot =  vb, 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 (5-54)
∂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

276 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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 =  mb, 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:

THEORY FOR THE SURFACE REACTIONS INTERFACE | 277

 ∂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 regard 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 5-53
and Equation 5-54, 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 5-53 and Equation 5-54, respectively:

∇ t ⋅ ( c s, i v t, mesh )

∇ t ⋅ ( c b, k v t, mesh )

278 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

THEORY FOR THE SURFACE REACTIONS INTERFACE | 279

 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.

280 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

THEORY FOR THE COUPLING OF MASS TRANSPORT TO ELECTROCHEMICAL REACTIONS | 281

282 | CHAPTER 5: CHEMICAL SPECIES TRANSPORT INTERFACES
 6

Fluid Flow Interfaces

This chapter describes the physics interfaces found under the Fluid 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 Laminar Flow and Creeping Flow Interfaces

• The Darcy’s Law Interface
• The Free and Porous Media Flow Interface
• The Brinkman Equations Interface
• Theory for the Laminar Flow and Creeping Flow Interfaces
• 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

| 283
 The Laminar Flow and Creeping Flow
Interfaces
In this section:

• The Creeping Flow Interface

• The Laminar Flow Interface
• Domain, Boundary, Pair, and Point Nodes for Single-Phase Flow

• Theory for the Laminar Flow and Creeping Flow Interfaces

In the COMSOL Multiphysics Reference Manual, see Table 2-4 for links to common
sections such as Discretization, Consistent Stabilization, Inconsistent Stabilization, and
Advanced Settings sections, some of them 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 Creeping Flow Interface

The Creeping Flow (spf) interface ( ) is used for simulating fluid flows at very low
Reynolds numbers for which the inertial term in the Navier–Stokes equations can be
neglected. Creeping flow, also referred to as Stokes flow, occurs in systems with high
viscosity or small geometrical length scales (for example, in microfluidics and MEMS
devices). The fluid can be compressible or incompressible, as well as Newtonian or
non-Newtonian.

The equations solved by the Creeping Flow interface are the Stokes equations for
conservation of momentum and the continuity equation for conservation of mass.

The Creeping Flow interface can be used for stationary and time-dependent analyses.

The main feature is the Fluid Properties node, which adds the Stokes equations and
provides an interface for defining the fluid material and its properties. Except where
noted below, see The Laminar Flow Interface for all other settings.

284 | CHAPTER 6: FLUID FLOW INTERFACES

PHYSICAL MODEL
By default, the Neglect inertial term (Stokes flow) check box is selected. If
unchecked,the inertial terms are included in the computations.

DISCRETIZATION
By default, the Creeping Flow interface uses P2+P1 elements. Contrary to general
laminar and turbulent single-phase flow simulations employing purely linear P1+P1
elements, P2+P1 elements are well suited for most creeping flow simulations but are
not in general fully conservative. Full conservation properties and high accuracy is
obtained by selecting P2+P2 or P3+P3 elements.

Note that P1+P1, P2+P2, and P3+P3 discretizations (the so-called equal order
interpolations) require streamline diffusion to be active.

The Laminar Flow Interface

The Laminar Flow (spf) interface ( ) is used to compute the velocity and pressure
fields for the flow of a single-phase fluid in the laminar flow regime. A flow remains
laminar as long as the Reynolds number is below a certain critical value. At higher
Reynolds numbers, disturbances have a tendency to grow and cause transition to
turbulence. This critical Reynolds number depends on the model, but a classical
example is pipe flow, where the critical Reynolds number is known to be approximately
2000.

The physics interface supports incompressible flow, weakly compressible flow (the
density depends on temperature but not on pressure), and compressible flow at low
Mach numbers (typically less than 0.3). It also supports flow of non-Newtonian fluids.

The equations solved by the Laminar Flow interface are the Navier–Stokes equations
for conservation of momentum and the continuity equation for conservation of mass.

The Laminar Flow interface can be used for stationary and time-dependent analyses.
Time-dependent studies should be used in the high-Reynolds number regime as these
flows tend to become inherently unsteady.

When the Laminar Flow interface is added, the following default nodes are also added
in the Model Builder: Fluid Properties, Wall (the default boundary condition is No slip),
and Initial Values. Other nodes that implement, for example, boundary conditions and
volume forces, can be added from the Physics toolbar or from the context menu
displayed when right-clicking Laminar Flow.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 285

 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. Physics interface variables can be referred to 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 spf.

About the Physics Interface Label Names

The label for a single-phase flow interface (the node name in the Model Builder) is
dynamic and is reset according to the turbulence model and the neglect inertial term
(Stokes flow) property set at the physics interface level. The availability also depends
on the software license.

If the Neglect inertial term (Stokes flow) check box is selected, then the Label changes
to Creeping Flow, which is the same Label that displays when that interface is added
from the Model Wizard or Add Physics window.

PHYSICAL MODEL

Compressibility
Depending of the fluid properties and the flow regime, three options are available for
the Compressibility option. In general the computational complexity increases from
Incompressible flow to Weakly compressible flow to Compressible flow (Ma<0.3) but the
underlying hypotheses are increasingly more restrictive in the opposite direction.

When the Incompressible flow option (default) is selected, the incompressible form of
the Navier–Stokes and continuity equations is applied. In addition, the fluid density is
evaluated at the Reference pressure level defined in this section. The Reference
temperature is set to 293.15 K.

The Weakly compressible flow option models compressible flow when the pressure
dependency of the density can be neglected. When selected, the compressible form of
the Navier–Stokes and continuity equations is applied. In addition, the fluid density is
evaluated at the Reference pressure level defined in this section.

When the Compressible flow (Ma<0.3) option is selected, the compressible form of the
Navier–Stokes and continuity equations is applied. Ma < 0.3 indicates that the inlet
and outlet conditions, as well as the stabilization, may not be suitable for transonic and
supersonic flow. For more information, see The Mach Number Limit.

286 | CHAPTER 6: FLUID FLOW INTERFACES

Neglect Inertial Term (Stokes Flow)
For low Reynolds number flows, the inertial terms in the Navier–Stokes equations may
be neglected.

Porous Media Domains

With the addition of various modules, the Enable porous media domains check box is
available. Selecting this option, a Fluid and Matrix Properties node, a Mass Source node,
and a Forchheimer Drag subnode are added to the physics interface. These are described
for the Brinkman Equations interface in the respective module’s documentation. The
Fluid and Matrix Properties can be applied on all domains or on a subset of the domains.

Include Gravity
When the Include gravity check box is selected, a global Gravity feature is shown in the
interface model tree, and the buoyancy force is included in the Navier–Stokes
equations.

Also, when the Include gravity check box is selected, the Use reduced pressure option
changes the pressure formulation from using the total pressure (default) to using the
reduced pressure. This option is suitable for configurations where the density changes
are very small; otherwise, the default formulation can be used. For more information,
see Gravity

Reference Values
Reference values are global quantities used to evaluate the density of the fluid when
the Incompressible flow or the Weakly compressible flow option is selected.

Reference pressure level There are generally two ways to include the pressure in fluid
flow computations: either to use the absolute pressure pA=p+pref, or the gauge
pressure p. When pref is nonzero, the physics interface solves for the gauge pressure
whereas material properties are evaluated using the absolute pressure. The reference
pressure level is also used to define the reference density.

Reference temperature The reference temperature is used to define the reference

density.

Reference position When Include gravity is selected, the reference position can be
defined. It corresponds to the location where the total pressure (that includes the
hydrostatic pressure) is equal to the Reference pressure level.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 287

 DEPENDENT VARIABLES
The following dependent variables (fields) are defined for this physics interface — the
Velocity field u and its components, and the Pressure p.

If required, the names of the field, component, and dependent variable can be edited.
Editing the name of a scalar dependent variable changes both its field name and the
dependent variable name. If a new field name coincides with the name of another field
of the same type, the fields share degrees of freedom and dependent variable names. A
new field name must not coincide with the name of a field of another type or with a
component name belonging to some other field. Component names must be unique
within a model except when two fields share a common field name.

CONSISTENT STABILIZATION
To enable this section, click the Show More Options button ( ) and select Stabilization
in the Show More Options dialog box.

There are two consistent stabilization methods: Streamline diffusion and Crosswind
diffusion. Usually, both check boxes for these methods are selected by default and
should remain selected for optimal performance. Consistent stabilization methods do
not perturb the original transport equation. Streamline diffusion must be selected
when using equal-order interpolation for pressure and velocity.

Select the Use dynamic subgrid time scale check box to approximate the time-scale
tensor in time dependent problems from projections of weak expressions. This check
box is selected by default. When not selected the actual time-step is used.

INCONSISTENT STABILIZATION
To enable this section, click the Show More Options button ( ) and select Stabilization
in the Show More Options dialog box.

There is usually just one inconsistent stabilization method — Isotropic diffusion. This
method is equivalent to adding a term to the diffusion coefficient in order to dampen
the effect of oscillations by making the system somewhat less dominated by
convection. If possible, minimize the use of the inconsistent stabilization method
because by using it you no longer solve the original problem. 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.

If required, select the Isotropic diffusion check box and enter a Tuning parameter δid as
a scalar positive value. The default value is 0.25 (a reasonable value to start with is

288 | CHAPTER 6: FLUID FLOW INTERFACES

roughly 0.5 divided by the element order). A higher value adds more isotropic
diffusion.

• Numerical Stability — Stabilization Techniques for Fluid Flow

ADVANCED SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box. Normally these settings do not
need to be changed.

The Use pseudo time stepping for stationary equation form is per default set to Automatic
from physics. This option can add pseudo time derivatives to the equation when the
Stationary equation form is used in order to speed up convergence. Pseudo time
stepping is triggered when the Laminar Flow interface is selected in some multiphysics
coupling features. Set Automatic from physics to On to apply pseudo time stepping also
for laminar flows. Set it to Off to disable pseudo time stepping completely.

When Use pseudo time stepping for stationary equation form is set to Automatic from
physics or On, 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.

The Use Block Navier-Stokes preconditioner in time dependent studies check box under
Linear solvers is available when the Compressibility option is set to Incompressible flow.
When this check box is selected, the default solver for time dependent study steps will
use the Block Navier-Stokes preconditioner in iterative solvers for the velocity and
pressure. Using this preconditioner may result in shorter solution times for large time
dependent problems with high Reynolds numbers.

• Pseudo Time Stepping for Laminar Flow Models

• Domain, Boundary, Pair, and Point Nodes for Single-Phase Flow
• Theory for the Laminar Flow and Creeping Flow Interfaces
• Block Navier-Stokes in the COMSOL Multiphysics Reference
Manual.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 289

 DISCRETIZATION
The default discretization for Laminar Flow is P1+P1 elements — that is, piecewise
linear interpolation for velocity and pressure. This is suitable for most flow problems.

Some higher-order interpolations are also available, and they can be cost-effective
options to obtain high accuracy for flows with low Reynolds numbers.

The P2+P2 and P3+P3 options, the equal-order interpolation options, are the preferred
higher-order options because they have higher numerical accuracy than the
mixed-order options P2+P1 and P3+P2. The equal-order interpolation options do,
however, require streamline diffusion to be active.

Flow Past a Cylinder: Application Library path COMSOL_Multiphysics/

Fluid_Dynamics/cylinder_flow

290 | CHAPTER 6: FLUID FLOW INTERFACES

Domain, Boundary, Pair, and Point Nodes for Single-Phase Flow
The following nodes, listed in alphabetical order, are 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).

• Boundary Stress • Periodic Flow Condition

• Flow Continuity • Point Mass Source1
• Fluid Properties • Pressure Point Constraint
• Gravity • Symmetry
• Initial Values • Volume Force
• Inlet • Wall
1
• Line Mass Source
• Open Boundary
• Outlet
1
A feature that may require an additional license

For 2D axisymmetric components, COMSOL Multiphysics takes the axial

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

In the COMSOL Multiphysics Reference Manual, see Table 2-4 for links to common
sections and Table 2-5 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
The Fluid Properties node adds the momentum and continuity equations solved by the
physics interface, except for volume forces, which are added by the Volume Force
feature. 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.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 291

 Temperature
By default, the Temperature model input is set to Common model input, and the
temperature is controlled from Default Model Inputs under Global Definitions or by a
locally defined Model Input. If a Heat Transfer interface is included in the component,
it controls the temperature Common model input. Alternatively, the temperature field
can be selected from another 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 for T.

You can also select User defined from the Temperature model input in order to manually
prescribe T.

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 or RANS 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.

Model Inputs and Multiphysics Couplings in the COMSOL Multiphysics

Reference Manual

292 | CHAPTER 6: FLUID FLOW INTERFACES

FLUID PROPERTIES

Density
The density can either be specified by a material, or by a User defined expression. The
density in a material can depend on temperature and pressure, and these dependencies
are automatically replaced by pref for weakly compressible flows and pref and Tref for
incompressible flows (as specified by the Compressibility setting at the physics interface
level). If density variations with respect to pressure are to be included in the
computations, Compressibility must be set to compressible. Any dependencies in the
density on quantities other than temperature and pressure must be consistent with the
Compressibility setting at the interface level.

Dynamic Viscosity
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.

Volume Force
The Volume Force node specifies the volume force F on the right-hand side of the
momentum equation.

∂u T 2
ρ + ρ ( u ⋅ ∇ )u = ∇ ⋅ – pI + μ ( ∇u + ( ∇u ) ) – --- μ ( ∇ ⋅ u )I + F
∂t 3

If several volume-force nodes are added to the same domain, then the sum of all
contributions are added to the momentum equation.

Initial Values
The initial values serve as initial conditions for a transient simulation or as an initial
guess for a nonlinear solver in a stationary simulation. Note that for a transient
compressible-flow simulation employing a material for which the density depends on
the pressure (such as air), discontinuities in the initial values trigger pressure waves
even when the Mach number is small. The pressure waves must be resolved and this
puts a restriction on the time step.

INITIAL VALUES
Initial values or expressions should be specified for the Velocity field u and the Pressure
p.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 293

 Wall
The Wall node includes a set of boundary conditions describing fluid-flow conditions
at stationary, moving, and leaking walls. For turbulent flow, the description may
involve wall functions and asymptotic expressions for certain turbulence variables.

BOUNDARY CONDITION
Select a Boundary condition for the wall.

• No Slip • Leaking Wall

• Slip • Navier Slip

No Slip
No slip is the default boundary condition to model solid walls. A no slip wall is a wall
where the fluid velocity relative to the wall velocity is zero. For a stationary wall that
means that u = 0.

The option for Porous treatment of no slip condition should be decided in Physical Model
when Enable porous media domains is activated. It specifies how Wall boundaries and
Interior Wall boundaries internal to porous domains are treated. When Standard no slip
formulation is chosen, a common no slip condition is applied on all solid walls. When
Porous slip is chosen, a blending analytic expression is instead applied on the
corresponding wall boundaries adjacent to the porous medium domain. It results in a
no slip condition in case the porous length scale is fully resolved by the mesh and a slip
condition in the opposite limit when the mesh is much coarser than the porous scale.
A smooth transition between these limits is ensured. Note that the interpretation and
usage of non-zero slip at the wall is the same as in the Navier Slip boundary condition.
By default, Velocity formulation is on and the treatment is based on an approximate
reconstruction of the far field pressure gradient using the slip velocity at the wall. If the
Pressure-gradient formulation is chosen, the local pressure gradient at the wall is
employed.

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.

294 | CHAPTER 6: FLUID FLOW INTERFACES

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.

Navier Slip
This boundary condition enforces no-penetration at the wall, u ⋅ n wall = 0 , and adds
a tangential stress

μ
K nt = – --- u slip
β

where K nt = K n – ( K n ⋅ n wall )n wall , K n = Kn wall and K is the viscous stress tensor.

β is a slip length, and u slip = u – ( u ⋅ n wall )n wall is the velocity tangential to the wall.

The Slip length setting is per default set to Factor of minimum element length. The slip
length β is then defined as β = f h h min , where h min is the smallest element side and
f h is a user input. Select User defined from the Slip length selection list in order to
manually prescribe β (SI unit: m).

In cases where the wall movement is nonzero, check Account for the translational wall
velocity in the friction force to use ( u – u bnd – ( ( u – u bnd ) ⋅ n wall )n wall ) instead of
u slip in the friction force.

The Navier slip option is not available when selecting a turbulence model.

WALL MOVEMENT
This section contains controls to describe the wall movement relative to the lab (or
spatial) frame.

The Translational velocity setting controls the translational wall velocity, utr. The list is
per default set to Automatic from frame. The physics automatically detects if the spatial
frame moves. This can for example happen if an ALE interface is present in the model
component. If there is no movement utr = 0. If the frame moves, utr becomes equal
to the frame movement. utr is accounted for in the actual boundary condition
prescribed in the Boundary condition section.

Select Zero (Fixed wall) from Translational velocity selection list to prescribe utr = 0.

Select Manual from Translational velocity selection list in order to manually prescribe
Velocity of moving wall, utr. This can for example be used to model an oscillating wall
where the magnitude of the oscillations are very small compared to the rest of the
model. Specifying translational velocity manually does not automatically cause the

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 295

 associated wall to move. An additional Moving Mesh node needs to be added from
Definitions to physically track the wall movement in the spatial reference frame.

The Sliding wall option is appropriate if the wall behaves like a conveyor belt with the
surface sliding in a tangential direction. A velocity is prescribed at the wall and the
boundary itself does not have to actually move relative to the reference frame.

• For 3D components, values or expressions for the Velocity of sliding wall uw should
be specified. If the velocity vector entered is not in the plane of the wall, COMSOL
Multiphysics projects it onto the tangential direction. Its magnitude is adjusted to
be the same as the magnitude of the vector entered.
• For 2D components, the tangential direction is unambiguously defined by the
direction of the boundary. For this reason, the sliding wall boundary condition has
different definitions in different space dimensions. A single entry for the Velocity of
the tangentially moving wall Uw should be specified in 2D.

CONSTRAINT SETTINGS
This section is displayed by clicking the Show More Options button ( ) and selecting
Advanced Physics Options in the Show More Options dialog box. The Constraints settings
can be set to Default, Use pointwise constraints, Use DG constraints, or Use weak
constraints. Use mixed constraints can be selected when imposing a no slip condition
exactly.

Depending on the constraint method selected, the following settings are available:

• Apply reaction terms on can be set to Individual dependent variables (default) or All
physics (symmetric). This setting is not available when Use DG constraints is selected.
• Select Elemental (default) or Nodal under Constraint method. This setting is not
available for Use DG constraints or Use weak constraints.

• Theory for the Wall Boundary Condition

• The Moving Mesh Interface in the COMSOL Multiphysics Reference
Manual

Inlet
This condition should be used on boundaries for which there is a net flow into the
domain. To obtain a numerically well-posed problem, it is advisable to also consider
the Outlet conditions when specifying an Inlet condition. For example, if the pressure

296 | CHAPTER 6: FLUID FLOW INTERFACES

is specified at the outlet, the velocity may be specified at the inlet, and vice versa.
Specifying the velocity vector at both the inlet and the outlet may cause convergence
difficulties.

BOUNDARY CONDITION
The available Boundary condition options for an inlet are Velocity, Fully developed flow,
and Pressure. After selecting a Boundary Condition from the list, a section with the same
or a similar name displays underneath. For example, if Velocity is selected, a Velocity
section, where further settings are defined, is displayed.

VELOCITY
The Normal inflow velocity is specified as u = −nU0, where n is the boundary normal
pointing out of the domain and U0 is the normal inflow speed.

The Velocity field option sets the velocity vector to u = u0. The components of the inlet
velocity vector u0 should be defined for this choice.

PRESSURE CONDITIONS
This option specifies the normal stress, which in most cases is approximately equal to
the pressure.

• For incompressible flow, the Pressure list has two options, Static and Total. For
weakly compressible and compressible flow, the static pressure should be specified
in the text field.
- If Pressure is Static, and the reference pressure pref, defined at the physics
interface level, is equal to 0, the value of the pressure p0, at the boundary, is the
absolute pressure. Otherwise, p0 is the relative pressure at the boundary.
- If Pressure is Total, the Average check box is available and unselected by default to
prescribe the total pressure pointwise. If it is selected, the averaged total pressure
is imposed in the weak forms instead.
When Include gravity is selected and Use reduced pressure not selected in the
interface Physical model section, the Compensate for hydrostatic pressure
approximation (named Compensate for hydrostatic pressure for incompressible flows)
check box is available and selected by default. When it is selected, the hydrostatic
pressure is automatically added to the pressure entered in p0 user input.
• The Suppress backflow option adjusts the inlet pressure locally in order to reduce the
amount of fluid exiting the domain through the boundary. If you clear the suppress
backflow option, the inlet boundary can become an outlet depending on the
pressure field in the rest of the domain.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 297

 • Flow direction controls in which direction the fluid enters the domain.
- For Normal flow, it prescribes zero tangential velocity component.
- For User defined, an Inflow velocity direction du (dimensionless) should be
specified. The magnitude of du does not matter, only the direction. du must
point into the domain.

MASS FLOW
The mass flow at an inlet can be specified by the Mass flow rate, the Pointwise mass flux,
the Standard flow rate, or the Standard flow rate (SCCM).

The Apply condition on each disjoint selection separately check box is selected per
default. When this setting is selected, the mass flow condition is applied separately on
each disjoint selection. If this option is not selected, the condition is applied over the
whole feature selection. The Apply condition on each disjoint selection separately should
be disabled only if the flow conditions are known to be identical on each disjoint
boundary.

Mass Flow Rate

The Mass flow rate option sets the integrated mass flow over the boundary selection,
the Normal mass flow rate to a specific value, m. The mass flow is assumed to be parallel
to the boundary normal, and the tangential flow velocity is set to zero.

For 2D components, the Channel thickness dbc is used to define the area across which
the mass flow occurs. This setting is not applied to the whole model. Line or surface
integrals of the mass flow over the boundary evaluated during postprocessing or used
in integration coupling operators do not include this scaling automatically. Such results
should be appropriately scaled when comparing them with the specified mass flow.

Pointwise Mass Flux

The Pointwise mass flux sets the mass flow parallel to the boundary normal. The
tangential flow velocity is set to zero. The mass flux is a model input, which means that
COMSOL Multiphysics can take its value from another physics interface when
available. When User defined is selected a value or function Mf should be specified for
the Mass flux.

Standard Flow Rate

The Standard flow rate Qsv sets a standard volumetric flow rate, according to the SEMI
standard E12-0303. The mass flow rate is specified as the volumetric flow rate of a gas
at standard density — the Mean molar mass Mn divided by a Standard molar volume Vm
(that is, the volume of one mole of a perfect gas at standard pressure and standard

298 | CHAPTER 6: FLUID FLOW INTERFACES

temperature). The flow occurs across the whole boundary in the direction of the
boundary normal and is computed by a surface (3D) or line (2D) integral. The
tangential flow velocity is set to zero.

The standard density can be defined directly, or by specifying a standard pressure and
temperature, in which case the ideal gas law is assumed. The options in the
Standard flow rate defined by list are:

• Standard density, for which the Standard molar volume Vm should be specified.
• Standard pressure and temperature, for which the Standard pressure Pst and the
Standard temperature Tst should be defined.

For 2D components, the Channel thickness dbc is used to define the area across which
the mass flow occurs. This setting is not applied to the whole model. Line or surface
integrals of the mass flow over the boundary evaluated during postprocessing or used
in integration coupling operators do not include this scaling automatically. Such results
should be appropriately scaled when comparing them with the specified mass flow.

Standard Flow Rate (SCCM)

The Standard flow rate (SCCM) boundary condition is equivalent to the Standard flow
rate boundary condition, except that the flow rate is entered directly in SCCMs
(standard cubic centimeters per minute) without the requirement to specify units.
Here, the dimensionless Number of SCCM units Qsccm should be specified.

FULLY DEVELOPED FLOW

The Fully developed flow option adds contributions to the inflow boundary, which force
the flow toward the solution for a fully developed channel flow. The channel can be
thought of as a virtual extrusion of the inlet cross section. The inlet boundary must
hence be flat in order for the fully developed flow condition to work properly. In 2D
axisymmetric models, the inlet normal must be parallel to the symmetry axis.

Select an option to control the flow rate at the inlet:

• Average velocity, Uav.

• Flow rate, V0. Two-dimensional models also require an Entrance thickness, Dz,
which is the out-of-plane thickness of the extruded entrance channel.
• Average pressure, Pav. Note that Pav is the average pressure on the inflow boundary.

The Apply condition on each disjoint selection separately check box is selected per
default. When this setting is selected, the fully developed flow condition is applied
separately on each disjoint selection. If this option is not selected, the condition is

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 299

 applied over the whole feature selection. The Apply condition on each disjoint selection
separately should be disabled only if the flow conditions are known to be identical on
each disjoint boundary.

The fully developed flow condition requires any volume force to be approximately
aligned with the normal of the inlet boundary. The exception is gravity when the
Include gravity setting is selected in the physics interface settings. Unless Use reduced
pressure is also selected, an option to Compensate for hydrostatic pressure or
Compensate for hydrostatic pressure approximation becomes available. It is selected per
default and should only be deselected if the inlet normal is aligned with the gravity
force and you want to specify an average pressure that includes the hydrostatic
pressure.

CONSTRAINT SETTINGS
This section is displayed by clicking the Show button ( ) and selecting Advanced
Physics Options.

• Prescribing Inlet and Outlet Conditions

• Normal Stress Boundary Condition

Fully Developed Flow (Inlet)

Outlet
This condition should be used on boundaries for which there is a net outflow from the
domain. To obtain a numerically well-posed problem, it is advisable to also consider
the Inlet conditions when specifying an Outlet condition. For example, if the velocity
is specified at the inlet, the pressure may be specified at the outlet, and vice versa.
Specifying the velocity vector at both the inlet and the outlet may cause convergence
difficulties. Selecting appropriate outlet conditions for the Navier–Stokes equations is
a nontrivial task. Generally, if there is something interesting happening at an outflow
boundary, the computational domain should be extended to include this
phenomenon.

300 | CHAPTER 6: FLUID FLOW INTERFACES

BOUNDARY CONDITION
The available Boundary condition options for an outlet are Pressure, Fully developed flow,
and Velocity.

PRESSURE CONDITIONS
This option specifies the normal stress, which in most cases is approximately equal to
the pressure. The tangential stress component is set to zero.

• For incompressible flow, the Pressure list has two options, Static and Total. For
weakly compressible and compressible flow, the static pressure should be specified
in the text field.
- If Pressure is Static, and the reference pressure pref, defined at the physics
interface level, is equal to 0, the value of the pressure p0, at the boundary, is the
absolute pressure. Otherwise, p0 is the relative pressure at the boundary.
- If Pressure is Total, the Average check box is available and selected by default to
prescribed the averaged total pressure in the weak forms. If it is unselected, the
total pressure is imposed pointwise.
When Include gravity is selected and Use reduced pressure not selected in the interface
Physical model section, the Compensate for hydrostatic pressure approximation (named
Compensate for hydrostatic pressure for incompressible flows) check box is available and
selected by default. When it is selected, the hydrostatic pressure is automatically added
to the pressure entered in p0 user input.

• The Normal flow option changes the no tangential stress condition to a no tangential
velocity condition. This forces the flow to exit (or enter) the domain perpendicularly
to the outlet boundary.
• The Suppress backflow check box is selected by default. This option adjusts the outlet
pressure in order to reduce the amount of fluid entering the domain through the
boundary.

VELOCITY
See the Inlet node Velocity section for the settings.

FULLY DEVELOPED FLOW

This boundary condition is applicable when the flow exits the domain into a long pipe
or channel, at the end of which a flow profile is fully developed.

The channel can be thought of as a virtual extrusion of the outlet cross section. The
outlet boundary must hence be flat in order for the fully developed flow condition to

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 301

 work properly. In 2D axisymmetric models, the outlet normal must be parallel to the
symmetry axis.

Select an option to control the flow rate at the outlet:

• Average velocity, Uav.

• Flow rate, V0. Two-dimensional models also require an Entrance thickness, Dz,
which is the out-of-plane thickness of the extruded entrance channel.
• Average pressure, Pav. Observe that Pav is the average pressure on the outflow.

The Apply condition on each disjoint selection separately check box is selected per
default. When this setting is selected, the fully developed flow condition is applied
separately on each disjoint selection. If this option is not selected, the condition is
applied over the whole feature selection. The Apply condition on each disjoint selection
separately should be disabled only if the flow conditions are known to be identical on
each disjoint boundary.

The fully developed flow condition requires any volume force to be approximately
aligned with the normal of the outlet boundary. The exception is gravity when the
Include gravity setting is selected in the physics interface settings. Unless Use reduced
pressure is also selected, an option to Compensate for hydrostatic pressure or
Compensate for hydrostatic pressure approximation becomes available. It is selected per
default and should only be deselected if the outlet normal is aligned with the gravity
force and you want to specify an average pressure that includes the hydrostatic
pressure.

A fully developed flow boundary cannot be adjacent to any Interior Wall feature.

CONSTRAINT SETTINGS
This section is displayed by clicking the Show button ( ) and selecting Advanced
Physics Options.

Prescribing Inlet and Outlet Conditions

Fully Developed Flow (Outlet)

302 | CHAPTER 6: FLUID FLOW INTERFACES

Symmetry
This node provides a boundary condition for symmetry boundaries. It should only be
used when the geometry and expected solution have mirror symmetry. By using
symmetries in a model its size can be reduced by one-half or more, making this an
efficient tool for solving large problems.

The Symmetry boundary condition prescribes no penetration and vanishing shear

stresses. The boundary condition is a combination of a Dirichlet condition and a
Neumann condition:

u ⋅ n = 0,  – pI +  μ ( ∇u + ( ∇u ) T ) – 2
--- μ ( ∇ ⋅ u )I  n = 0
  3 

u ⋅ n = 0, ( – pI + μ ( ∇u + ( ∇u ) T ) )n = 0

for the compressible and incompressible formulations. The Dirichlet condition takes
precedence over the Neumann condition, and the above equations are equivalent to
the following equation for both the compressible and incompressible formulations:

u ⋅ n = 0, K – ( K ⋅ n )n = 0
K = μ ( ∇u + ( ∇u ) T )n

BOUNDARY SELECTION
For 2D axial symmetry, a boundary condition does not need to be defined for the
symmetry axis at r = 0. The software automatically provides a condition that prescribes
ur = 0 and vanishing stresses in the z direction and adds an Axial Symmetry node that
implements these conditions on the axial symmetry boundaries only.

CONSTRAINT SETTINGS
This section is displayed by clicking the Show button ( ) and selecting Advanced
Physics Options.

Open Boundary
The Open Boundary condition describes boundaries in contact with a large volume of
fluid. Fluid can both enter and leave the domain on boundaries with this type of
condition.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 303

 BOUNDARY CONDITIONS
The Boundary condition options for open boundaries are Normal stress and No viscous
stress.

Normal Stress
The Normal stress f0 condition implicitly imposes p ≈ f 0 .

No Viscous Stress
The No Viscous Stress condition specifies vanishing viscous stress on the boundary. This
condition does not provide sufficient information to fully specify the flow at the open
boundary and must at least be combined with pressure constraints at adjacent points.

The No viscous stress condition prescribes:

 μ ( ∇u + ( ∇u ) T ) – 2
--- μ ( ∇ ⋅ u )I n = 0
 3 

μ ( ∇u + ( ∇u ) T )n = 0

for the compressible and the incompressible formulations. This condition can be useful
in some situations because it does not impose any constraint on the pressure. A typical
example is a model with volume forces that give rise to pressure gradients that are hard
to prescribe in advance. To make the model numerically stable, this boundary
condition should be combined with a point constraint on the pressure.

Boundary Stress
The Boundary Stress node adds a boundary condition that represents a general class of
conditions also known as traction boundary conditions.

BOUNDARY CONDITION
The Boundary condition options for the boundary stress are General stress, Normal
stress, and Normal stress, normal flow.

General Stress
When General stress is selected, the components for the Stress F should be specified.
The total stress on the boundary is set equal to the given stress F:

 – pI +  μ ( ∇u + ( ∇u ) T ) – 2
--- μ ( ∇ ⋅ u )I  n = F
  3 

( – pI + μ ( ∇u + ( ∇u ) T ) )n = F

304 | CHAPTER 6: FLUID FLOW INTERFACES

for the compressible and the incompressible formulations.

This boundary condition implicitly sets a constraint on the pressure that for 2D flows is

∂u n
p = 2μ ---------- – n ⋅ F (6-1)
∂n

If ∂un/∂n is small, Equation 6-1 states that p ≈ −n·F.

Normal Stress
Normal Stress is described for the Open Boundary node.

Normal Stress, Normal Flow

For Normal stress, normal flow, the magnitude of the Normal stress f0 should be
specified. The tangential velocity is set to zero on the boundary:

n  – pI +  μ ( ∇u + ( ∇u ) T ) – --- μ ( ∇ ⋅ u )I  n = – f 0 ,
T 2
t⋅u = 0
  3 

T
n ( – pI + μ ( ∇u + ( ∇u ) T ) )n = – f 0 , t⋅u = 0

for the compressible and the incompressible formulations.

This boundary condition implicitly sets a constraint on the pressure that for 2D flows is

∂u n
p = 2μ ---------- + f 0 (6-2)
∂n

If ∂un/∂n is small, Equation 6-2 states that p ≈ f0.

CONSTRAINT SETTINGS
This section is displayed by clicking the Show button ( ) and selecting Advanced
Physics Options.

If Normal Stress, Normal Flow is selected as the Boundary condition, then to Apply
reaction terms on all dependent variables, the All physics (symmetric) option should be
selected. Alternatively, the Individual dependent variables could be selected to restrict
the reaction terms as needed.

Periodic Flow Condition

The Periodic Flow Condition splits its selection into a source group and a destination
group. Fluid that leaves the domain through one of the destination boundaries enters

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 305

 the domain through the corresponding source boundary. This corresponds to a
situation where the geometry is a periodic part of a larger geometry. If the boundaries
are not parallel to each other, the velocity vector is automatically transformed.

If the boundaries are curved, the orientation of the source must be specified manually
(see Orientation of Source).

No input is required when Compressible flow (Ma<0.3) is selected for Compressibility

under the Physical Model section for the physics interface. Typically when a periodic
boundary condition is used with a compressible flow, the pressure is the same at both
boundaries and the flow is driven by a volume force.

FLOW CONDITION
This section is available when Incompressible flow is selected for Compressibility under
the Physical Model section for the physics interface.

The Flow Condition at the boundary is specified through a value or expression for either
·
the Pressure difference, p src – p dst , or the Mass flow, m . The mass flow option ensures
a pressure difference is achieved across the source and destination boundaries. This
pressure difference can, for example, drive the fully developed flow in a channel.

To set up a periodic boundary condition, both boundaries must be selected in the

Periodic Flow Condition node. COMSOL Multiphysics automatically assigns one
boundary as the source and the other as the destination. To manually set the
destination selection, a Destination Selection subnode is available from the context
menu (by right-clicking the parent node) or from the Physics toolbar, Attributes menu.
All destination sides must be connected.

CONSTRAINT SETTINGS
This section is displayed by clicking the Show button ( ) and selecting Advanced
Physics Options.

ORIENTATION OF SOURCE
For information about the Orientation of Source section, see Orientation of Source and
Destination in the COMSOL Multiphysics Reference Manual.

Flow Continuity
The Flow Continuity condition is suitable for pairs where the boundaries match; it
prescribes that the flow field is continuous across the pair.

306 | CHAPTER 6: FLUID FLOW INTERFACES

The parts of the boundary where a source boundary lacks a corresponding destination
boundary and vice versa will get conditions from other boundary conditions under the
physics interface acting as fallback boundary conditions on the nonoverlapping parts.
By default, the Wall node is used as fallback unless another feature has been selected
for the boundary.

About Identity and Contact Pairs

Pressure Point Constraint

The Pressure Point Constraint condition can be used to specify the pressure level. If it
is not possible to specify the pressure level using a boundary condition, the pressure
level must be set in some other way, for example, by specifying a fixed pressure at a
point.

PRESSURE CONSTRAINT
The relative pressure value is set by specifying the Pressure p0. If the reference pressure
pref defined at the physics interface level is equal to zero, p0 represents the absolute
pressure.

CONSTRAINT SETTINGS
This section is displayed by clicking the Show button ( ) and selecting Advanced
Physics Options.

The Apply reaction terms on setting is set per default to Individual dependent variables.
All physics (symmetric) cannot be used together with a segregated solver when fluid
flow is coupled with Moving Mesh, Level Set, or Phase Field.

Point Mass Source

This feature requires at least one of the following licenses: Battery Design Module,
CFD Module, Chemical Reaction Engineering Module, Corrosion Module,
Electrochemistry Module, Electrodeposition Module, Fuel Cell & Electrolyzer
Module, Microfluidics Module, Pipe Flow Module, or Subsurface Flow Module.

The Point Mass Source feature models mass flow originating from an infinitely small
domain centered around a point.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 307

 For the Reacting Flow in Porous Media, Diluted Species interface, which is available
with the CFD Module, Chemical Reaction Engineering Module, or Battery Design
Module, there are two nodes: one for the fluid flow (Fluid Point Source) and one for
the species (Species Point Source).

SOURCE STRENGTH
·
The source Mass flux, q p should be specified. A positive value results in mass being
ejected from the point into the computational domain. A negative value results in mass
being 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 a point source located on a symmetry
plane has twice the given strength.

Mass Sources for Fluid Flow in the COMSOL Multiphysics Reference

Manual

Line Mass Source

This feature requires at least one of the following licenses: Battery Design Module,
CFD Module, Chemical Reaction Engineering Module, Corrosion Module,
Electrochemistry Module, Electrodeposition Module, Fuel Cell & Electrolyzer
Module, Microfluidics Module, Pipe Flow Module, or Subsurface Flow Module.

The Line Mass Source feature models mass flow originating from a tube region with
infinitely small radius.

For the Reacting Flow in Porous Media, Diluted Species interface, which is available
with the CFD Module, Chemical Reaction Engineering Module, or Battery Design
Module, there are two nodes, one for the fluid flow (Fluid Line Source) and one for the
species (Species Line Source).

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

308 | CHAPTER 6: FLUID FLOW INTERFACES

MODEL DIMENSION APPLICABLE GEOMETRICAL ENTITY

2D Axisymmetry Points not on the axis of symmetry

3D Edges

SOURCE STRENGTH
·
The source Mass flux, q l , should be specified. A positive value results in mass being
ejected from the line into the computational domain and a negative value means that
mass is removed from the computational domain.

Line sources located on a boundary affect the adjacent computational domains. This,
for example, has the effect that a line source located on a symmetry plane has twice the
given strength.

Mass Sources for Fluid Flow in the COMSOL Multiphysics Reference

Manual

Gravity
The Gravity global feature is automatically added when Include gravity is selected at the
interface level in the Physical Model settings. It defines the gravity forces from the
Acceleration of gravity value. When a turbulence model that solves for the turbulent
kinetic energy, k, is used, the option Include buoyancy-induced turbulence is available.
When selected, the Buoyancy contribution is by default set to Automatic from
multiphysics. Contributions are only obtained from multiphysics couplings that
support buoyancy-induced turbulence, such as Nonisothermal Flow. If the Buoyancy
contribution is switched to User defined, a text field for the Turbulent Schmidt number
appears.

ACCELERATION OF GRAVITY
The Acceleration of gravity (SI unit m/s, default value −gconstez in 2D axial symmetry
and 3D and −gconstey in 2D) is used to define the gravity forces. It should be a global
quantity.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 309

 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 Porous Medium Properties node, which provides interfaces for
defining the fluid material and the porous matrix properties.

When this physics interface is added, the following default nodes are also added in the
Model Builder — Porous Medium, 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].

GRAVITY EFFECTS
By default there are no gravity effects added to Darcy’s Law interface. Select the check
box Include gravity to activate the acceleration of gravity. When this check box is
selected a global Gravity feature node is shown in the interface model tree.

310 | CHAPTER 6: FLUID FLOW INTERFACES

Enter a value for the acceleration of gravity. The default value g_const is the
predefined standard acceleration of gravity on Earth.

This feature requires a specific license. For a detailed overview of the

functionality available in each product, visit [Link]
products/specifications/.

DISCRETIZATION
To display all settings available in this section, click the Show More Options button ( )
and select Advanced Physics Options in the Show More Options dialog box.

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.

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 postprocessing 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.

THE DARCY’S LAW INTERFACE | 311

 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.

• 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

• Species Transport in the Gas Diffusion Layers of a PEM: Application

Library path Fuel_Cell_and_Electrolyzer_Module/Fuel_Cells/
pem_gdl_species_transport_2d
• Steam Reformer: Application Library path
Chemical_Reaction_Engineering_Module/Reactors_with_Porous_Catalysts/
steam_reformer
• Terzaghi Compaction: Application Library path
Subsurface_Flow_Module/Flow_and_Solid_Deformation/
terzaghi_compaction

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 are 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).

312 | CHAPTER 6: FLUID FLOW INTERFACES

DOMAIN

• Porous Medium • Mass Source

• Gravity • Thickness
• Cross Section • Porous Electrode Coupling
• Initial Values • Unsaturated Porous Medium

Note that some features are only available with certain COMSOL products (see
[Link]

BOUNDARY, EDGE, AND POINT

The following nodes (listed in alphabetical order) are available on exterior boundaries:

• Atmosphere/Gauge • Outlet
• Electrode-Electrolyte Interface • Pervious Layer
Coupling • Point Mass Source
• Flux Discontinuity • Precipitation
• Fracture Flow • Pressure
• Hydraulic Head • Pressure Head
• Inlet • Reaction Coefficients1
• Interior Wall • Symmetry
• Line Mass Source • Thin Barrier
• Mass Flux
• No Flow
1
This node is described for the Transport of Diluted Species Interface

Note that some features are only available with certain COMSOL products (see
[Link]

The relevant physics interface condition at interior boundaries is continuity:

n ⋅ ( ρ1 u1 –ρ2 u2 ) = 0

THE DARCY’S LAW INTERFACE | 313

 The continuity boundary condition ensures that the pressure and mass flux are
continuous. In addition, the Pressure boundary condition is available on interior
boundaries.

The continuity boundary condition provides continuity for the pressure and mass flux.
In addition, the following boundary conditions are available on interior boundaries:

• Pressure • Pervious Layer

• Pressure Head • Flux Discontinuity
• Hydraulic Head • Fracture Flow
• Interior Wall • Thin Barrier

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 2-4 for links
to common sections and Table 2-5 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.

Porous Medium
The Porous Medium node adds the equations for modeling flow through porous
domains. By default these are Equation 6-3 and Equation 6-4 (excluding any mass
sources).

∂
( ε ρ ) + ∇ ⋅ ( ρu ) = Q m (6-3)
∂t p

314 | CHAPTER 6: FLUID FLOW INTERFACES

 κ
u = – --- ∇p (6-4)
μ

For a steady-state problem the first term in Equation 6-3 disappears. When Gravity is
active Equation 6-4 is of the following form:

κ
u = – --- ( ∇p + ρg ) (6-5)
μ

The Porous Medium feature has two default subfeatures — the Fluid subfeature where
the fluid density ρ(SI unit: kg/m3) and dynamic viscosity μ (SI unit: Pa·s) are defined
and the Porous Matrix subfeature where the permeability κ (SI unit: m2) and porosity
εp (dimensionless) are specified.

COORDINATE SYSTEM SELECTION

Select a coordinate system from the Coordinate system list for the interpretation of
directions in anisotropic material properties. The default is the Global coordinate
system, and the list contains any additional orthonormal coordinate system (except
boundary coordinate systems) added under the Definitions node.

The subnodes inherit these coordinate system settings. In particular, the Permeability
or Hydraulic conductivity (in the Porous Matrix subnode) should be set according to
the coordinate system selected in this section.

FLOW MODEL
Define if the flow follows a linear or nonlinear pressure-velocity relationship.

• Darcian flow (default) defines a linear relationship using Equation 6-3 and
Equation 6-4.
• Non-Darcian flow defines a nonlinear relationship using Equation 6-3 and

μ
∇p = – --- u – βρ u u
κ

where the nonlinear parameter β (SI unit: 1/m) is further specified in the Porous
Matrix subfeature.

STORAGE MODEL
Equation 6-3 can also be formulated with respect to a storage term.

∂p κ
ρS ------ + ∇ ⋅ ρ – --- ( ∇p ) = Q m (6-6)
∂t μ

THE DARCY’S LAW INTERFACE | 315

 The storage coefficient S can be interpreted as the weighted compressibility of the
porous material and the fluid. Define the time dependent storage term by selecting one
of the following options from the drop-down menu:

• From density and porosity (default), uses the formulation of Equation 6-3
• Linearized storage, where the following linear equation is used to define the storage:
S = ε p χ f + ( 1 – ε p )χ p

• Poroelastic storage, where S = εpχf

• Quasistatic, where the storage term is set to zero
• User defined to directly specify the storage coefficient S

Note that the option to choose a different Flow model and Storage model is only
available in some modules. For a detailed overview of the functionality available in each
product, visit [Link]

• Porous Material in the COMSOL Multiphysics Reference Manual

• About Darcian and Non-Darcian Flow in the Porous Media Flow
Module User’s Guide
• Storage Model in the Subsurface Flow Module User’s Guide

Fluid
This node defines the material properties of the fluid of the Porous Medium or
Unsaturated Porous Medium parent node. The fluid can be specified as general gas or
liquid or as an ideal gas.

MODEL INPUT
This section contains fields and values that are inputs for expressions defining material
properties. If such user-defined property groups are added, the model inputs appear
here.

FLUID PROPERTIES
The available options for the Fluid type are Gas/Liquid (default) or Ideal gas. The
selection determines how the density and compressibility of the fluid are set. The latter
is only required if a poroelastic or linearized storage model has been selected in the
parent Porous Medium node. For all fluid types specify the dynamic viscosity μ (SI
unit: Pa·s).

316 | CHAPTER 6: FLUID FLOW INTERFACES

Gas/Liquid
This option specifies the Density and the Compressibility for a general gas or liquid.

Ideal Gas
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.

If required by a Storage Model, the Compressibility of the ideal gas is calculated as

χ f = 1 ⁄ p A with the absolute pressure pA (Pa).

Porous Matrix
This node defines the porosity and material properties of the solid matrix of the Porous
Medium or Unsaturated Porous Medium parent node.

MODEL INPUT
This section contains fields and values that are inputs for expressions defining material
properties. If such user-defined property groups are added, the model inputs appear
here.

MATRIX PROPERTIES
The default Porosity εp of the solid matrix is taken From material. In a Porous Material
node, the porosity is defined as follows:

εp = 1 –  θsi – θimfi
i i

where θsi and θimfi are the porosities of the Solid and Immobile Fluids subnodes under
the Porous Material node. See Porous Material in the COMSOL Multiphysics
Reference Manual for more information.

Select User defined to enter a value or expression for εp.

If required by a Storage model in the parent node, specify the Effective compressibility
–4
of the porous matrix. The default value is χ p = 10 Pa .

Select a Permeability model to specify the capacity of the porous material to transmit
flow. Which options are available depends on the Flow model setting in the parent node.

THE DARCY’S LAW INTERFACE | 317

 Note that for the Unsaturated Porous Medium parent node only the Darcian Flow
models are available.

Darcian Flow
If Darcian flow is selected in the parent Porous medium node, select between the
following options for the Permeability model:

• Select Permeability (default) to define the permeability of the porous matrix. The
default Permeability κ (SI unit: m2) uses the value From material, as defined by the
Porous material. For User defined select Isotropic to define a scalar value or Diagonal
or Symmetric to define a tensor value.
• Select Hydraulic conductivity or define a combination of fluid permeability and
dynamic viscosity. For Hydraulic conductivity K (SI unit: m/s) select Isotropic to
define a scalar value or Diagonal or Symmetric to define a tensor value. The default is
2.94·10−4 m/s.
• Select Kozeny-Carman to define the permeability from the porosity and mean particle
diameter. Enter the mean Particle diameter dp (SI unit: m), the default value is
0.5 mm.

Non-Darcian Flow
Select between the following options for the Permeability model:

• For Forchheimer, the default Permeability κ (SI unit: m2) uses the value From
material, as defined by the Porous material list. Furthermore, the dimensionless
Forchheimer parameter cF can be defined. The default value is 0.55.
• If Ergun is selected, enter the mean Particle diameter dp (default value: 0.5 mm).
• For Burke–Plummer, specify the mean Particle diameter dp (default value: 0.5 mm).
• For Klinkenberg, the default Permeability κ∞ (SI unit: m2) uses the value From
material. Enter the Klinkenberg parameter bK. Its default value is 1e3 Pa.

Note that some options are only available in some modules. For a detailed overview of
the functionality available in each product, visit [Link]
specifications/.

• About Darcian and Non-Darcian Flow in the Porous Media Flow

Module User’s Guide
• Permeability Models in the Porous Media Flow Module User’s Guide

318 | CHAPTER 6: FLUID FLOW INTERFACES

RETENTION MODEL
For an Unsaturated Porous Medium select between the following options for the
retention model:

• van Genuchten, to specify the retention model using the van Genuchten relationship.
Enter the constitutive relation constants α (default is 1, and the SI unit is 1/m), n
(default is 2), and l (default is 0.5). The constitutive parameter m is equal to 1 − 1/n.
• Brooks and Corey to use the retention model according to the Brooks and Corey
relationships.
• User defined to use a different retention model. Enter user defined expressions for
the Effective saturation Se, the Liquid volume fraction θl. The default is εp (the
porosity variable). Specify the Specific moisture capacity Cm (SI unit: 1/m). The
default is 0 (1/m). Enter an expression for th Relative permeability κr. The default
is 1.

If there is a residual volume of liquid that cannot move through the pore network, also
enter a a value between 0 and 1 for the Residual liquid volume fraction θr. The default
value is 0.

Retention and Permeability Relationships in the Subsurface Flow Module

User’s Guide

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 6-3).

∂ ( ρε ) + ∇ ⋅ ( ρu )
= Qm (6-7)
∂t

For — which is available for the Subsurface Flow Module and the Porous Media Flow
Module — the mass source is applicable to the right-hand side of (where it is
multiplied with the fracture thickness).

MASS SOURCE
Enter a value or expression for the Mass source Qm (SI unit: kg/(m3·s)). The default is
0 kg/(m3·s).

THE DARCY’S LAW INTERFACE | 319

 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.

If you have the Subsurface Flow Module licensed, you can specify the pressure either
directly or as an expression for the pressure head, Hp, or the hydraulic head, H; the
hydraulic head and the pressure head relate to the pressure p as

p
H p = ------ ; H = Hp + D
ρg

where ρ is the fluid density (SI unit: kg/m3); g denotes the acceleration of gravity
(SI unit: m/s2); and D is the elevation (SI unit: m).

INITIAL VALUES
Enter a value or expression for the initial value of the Pressure p (SI unit: Pa). The
default value is 0 Pa.

In case the Subsurface Flow Module is available, click the Pressure head button to enter
a value or expression for Hp (SI unit: m). The default is 0 m. Click the Hydraulic head
button to enter a value or expression for H (SI unit: m). The default is 0 m.

FRACTURE FLOW
For the Fracture Flow Interface, enter a value or expression for the Fracture thickness
df (SI unit: m). The default is 0.1 m.

Flow in a Fractured Reservoir: Application Library path

Subsurface_Flow_Module/Fluid_Flow/fractured_reservoir_flow

Unsaturated Porous Medium

The Unsaturated Porous Medium node adds the Richards’ equation (Equation 6-8) for
flow in variably saturated porous media.

Cm ∂p κr κ
ρ  -------- + S e S p ------ + ∇ ⋅ ρ  – -------- ( ∇p + ρ g ∇D ) = Q m (6-8)
ρg ∂t μ

The Unsaturated Porous Medium feature has two default subfeatures — the Fluid
subfeature where the fluid density ρ(SI unit: kg/m3) and viscosity μ (SI unit: Pa·s) are

320 | CHAPTER 6: FLUID FLOW INTERFACES

defined and the Porous Matrix subfeature where the permeability κ (SI unit: m2)and
porosity εp (dimensionless) are specified as well as the retention model.

COORDINATE SYSTEM SELECTION

Select a coordinate system from the Coordinate system list for the interpretation of
directions in anisotropic material properties. The default is the Global coordinate
system, and the list contains any additional orthonormal coordinate system (except
boundary coordinate systems) added under the Definitions node.

The subnodes inherit these coordinate system settings. In particular, the Permeability
or Hydraulic conductivity (in the Porous Matrix subnode) should be set according to
the coordinate system selected in this section.

STORAGE MODEL
With this option, define the time storage term Sp in Equation 6-8.

• From density and porosity

• Linearized storage (default)
• User defined

This feature requires a specific license. For a detailed overview of the functionality
available in each product visit [Link]

Gravity
The Gravity node is automatically added when Include gravity is selected at interface
level in the Darcy’s Law settings and it is active in all domains in which the Darcy’s Law
interface is applied.

This feature requires a specific license. For a detailed overview of the functionality
available in each product visit [Link]

COORDINATE SYSTEM SELECTION

The Global coordinate system is selected by default. The Coordinate system list contains
any additional coordinate systems that the model includes. It can be used when
prescribing the direction of the gravitational forces.

GRAVITY
Specify either the acceleration vector or — in case you have a Subsurface Flow Module
license — the elevation.

THE DARCY’S LAW INTERFACE | 321

 When Acceleration is selected from the list, enter the components of the Gravity vector
g. The default value is g_const which is the physical constant having the value
9.8066 m/s2.

• For 3D and 2D axisymmetric models, the default value is -g_const in the

z direction.
• For 2D models, the default value is -g_const in the y direction.

When Elevation is selected from the list, specify the Elevation D (SI unit: m). Select the
check box Specify reference position to define a reference elevation.

Select the acceleration of gravity from either the Darcy’s Law interface Settings
(default), or specify a user defined value. When the check box Include gravity is not
selected in the Darcy’s Law interface Settings, the elevation D is set equal to zero.

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
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.

322 | CHAPTER 6: FLUID FLOW INTERFACES

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.

This feature requires a specific license. For a detailed overview of the functionality
available in each product visit [Link]

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.

This feature requires a specific license. For a detailed overview of the functionality
available in each product visit [Link]

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 DARCY’S LAW INTERFACE | 323

 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).

For the Subsurface Flow Module, the Pressure node provides the pressure P0 as a
condition on edges in 3D models. Then select the edges under Edge Selection.

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

Pressure constraint on edges are available for use with the Fracture Flow boundary
condition (which is available in the Subsurface Flow Module). This boundary
condition needs constraints on the edges surrounding the fracture-flow boundary. In
other cases, pressure constraints on edges are not implemented.

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 + ρ g ∇D ) = N 0
μ

where N0 is a value or expression for the specified inward (or outward) Darcy flux. D
is the elevation head which is set to zero for other than Subsurface Flow Module
applications.

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)).

324 | CHAPTER 6: FLUID FLOW INTERFACES

Line Mass Source
The Line Mass Source node adds mass flow originating from a tube of infinitely small
radius.

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
3D Edges

LINE MASS SOURCE

Enter a value or expression for the source strength, N0 (SI unit: kg/(m·s)). A positive
value results in mass injection from the line into the computational domain, and a
negative value means that the mass 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.

Point Mass Source

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.

POINT MASS SOURCE

Enter a value or expression for the source strength, N0 (SI unit: kg/(s)). A positive
value results in mass injection from the point into the computational domain, and a
negative value means that the mass 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 DARCY’S LAW INTERFACE | 325

 Inlet
The Inlet node adds a boundary condition for the inflow (or outflow) perpendicular
(normal) to the boundary. It has three options that can be used to specify inlet
condition on a boundary, as follows:

VELOCITY
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. The inlet velocity boundary condition is implemented as;

κ
n ⋅ ρ --- ( ∇p + ρ g ∇D ) = 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. D is the elevation head which is set to zero for
other than Subsurface Flow Module applications.

PRESSURE
Use the Pressure option to specify the inlet 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. Enter a value or expression for the Pressure p0(SI unit: Pa).

MASS FLOW
If you select Mass flow as the inlet condition, specify the total Mass flow rate M0(SI unit:
kg/s), or the Pointwise mass flux N0(SI unit: kg/(m2·s)).

With Mass flow rate boundary condition, positive values correspond to flow into the
model domain:

–  ρ ( u ⋅ n ) dS = M0
∂Ω

where M0 is a value or expression for the specified inward (or outward) Darcy flux.

Pointwise mass flux boundary condition, positive values correspond to flow into the
model domain:

κ
n ⋅ ρ --- ( ∇p + ρ g ∇D ) = N 0
μ

326 | CHAPTER 6: FLUID FLOW INTERFACES

where N0 is a value or expression for the specified inward (or outward) Darcy flux.

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

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

κ
n ⋅ --- ( ∇p + ρ g ∇D ) = 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
impermeable boundaries. The mathematical formulation is:

κ
n ⋅ ρ --- ( ∇p + ρ g ∇D ) = 0
μ

where n is the vector normal to the boundary. D is the elevation head which is set to
zero for any other than Subsurface Flow Module applications.

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 6-9) and N0 is a specified value or expression for the flux discontinuity.

THE DARCY’S LAW INTERFACE | 327

 κ
u = – --- ∇p (6-9)
μ

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. It has different options that can be used to specify inlet
condition on a boundary, as follows:

VELOCITY
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.

κ
– n ⋅ ρ --- ∇p = ρU 0
μ

where U0 is a specified value or expression for the outward (or inward) Darcy velocity.

PRESSURE
Similar to the inlet Pressure option, the outlet pressure on a boundary can be specified.
Enter a value or expression for the Pressure p0(SI unit: Pa).

DISCHARGE
Enter a value or expression for the discharge QD to specify the volumetric flow rate
through the boundary. The mass flux ρu is related to the discharge as follows:

 ρu ⋅ ds = ρQD . (6-10)
∂Ω

The mean normal outflow velocity at the boundary can then be calculated as Uout =
QD/A, where A is the cross sectional area of the boundary.

328 | CHAPTER 6: FLUID FLOW INTERFACES

Note that this option is only available for Porous Media Flow and Subsurface Flow
modules. For a detailed overview of the functionality available in each product visit
[Link]

Precipitation
Enter a value or expression for the Precipitation rate which then contributes to the mass
flux at the boundaries selected. If the boundary is inclined, a Slope correction can be
applied.

This feature requires a specific license. For a detailed overview of the functionality
available in each product visit [Link]

Interior Wall
The Interior Wall boundary condition can only be applied on interior boundaries. It is
similar to the No Flux boundary available on exterior boundaries except that it applies
on both sides of an interior boundary. It allows discontinuities of velocity and pressure
across the boundary. The Interior Wall boundary condition can be used to avoid
meshing thin structures by applying no-flux condition on interior curves and surfaces
instead.

This feature requires a specific license. For a detailed overview of the functionality
available in each product visit [Link]

Thin Barrier
The Thin Barrier boundary condition models interior permeable walls, membranes,
geotextiles, or perforated plates as thin permeable barriers. The Thin Barrier boundary
condition can only be applied on interior boundaries.

This feature requires a specific license. For a detailed overview of the functionality
available in each product visit [Link]

WALL
Enter a value or expression for the Thickness db (SI unit: m, the default is 0.1 m) and
for the Permeability κb (SI unit: m2). The default Permeability κb uses the value From
material. For User defined select Isotropic to define a scalar value or Diagonal, Symmetric,
or Full to define a tensor value and enter another value or expression in the field or
matrix.

THE DARCY’S LAW INTERFACE | 329

 Pressure Head
Use the Pressure Head node to specify the pressure head (instead of the pressure) on a
boundary. It adds this boundary condition for the pressure head Hp= Hp0, where Hp0
is a known pressure head given as a number, a distribution, or an expression involving
time, t, for example. The dimension of the pressure head is length (SI unit: m).

The Subsurface Flow Module license is required to use this boundary condition (see
[Link]

PRESSURE HEAD
Enter a value or expression for the Pressure head Hp0 (SI unit: m). The default is 0 m.

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

Hydraulic Head
Use the Hydraulic Head node to specify the hydraulic head (instead of the pressure) on
a boundary. This adds the Dirichlet condition for the hydraulic head H = H0 where H0
is a known hydraulic head given as a number, a distribution, or an expression involving
time, t, for example.

The Subsurface Flow Module license is required to use this boundary condition (see
[Link]

HYDRAULIC HEAD
Enter a value or expression for the Hydraulic head H0 (SI unit: m). The default is 0 m.

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

Atmosphere/Gauge
The Atmosphere/Gauge node specifies an atmospheric pressure or gauges the pressure
to the atmospheric value. This means that the total hydraulic potential reduces to the
gravitational pressure at the free surface. At a free surface, such as a spring or a seepage
face, the pressure is atmospheric. If the pressures in the model is gauged to the

330 | CHAPTER 6: FLUID FLOW INTERFACES

atmospheric value (p = 0), the total hydraulic potential reduces to the gravitational
potential at the free surface — for example, the height of the free surface multiplied by
the fluid weight, or ρf gD. This boundary condition sets the pressure at the boundary
to zero and p = 0.

The Subsurface Flow Module license is required to use this boundary condition (see
[Link]

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

Pervious Layer
The Subsurface Flow Module license is required to use this boundary condition (see
[Link]

The Pervious Layer node provides a boundary condition that describes a mass flux
through a semi-pervious layer connected to an external fluid source at different
pressure, pressure head, or hydraulic head. The model domain might connect to a
larger body of water through the semi-pervious layer. This condition is represented
with the following boundary condition:

κ ( pb – p )
n ⋅ ρ --- ( ∇p + ρ g ∇D ) = ρR b -------------------- + ( D b – D ) (6-11)
μ ρg

In this equation, pb (SI unit: Pa) and Db (SI unit: m) are the pressure and the elevation
of the distant fluid source, respectively, and Rb (SI unit: 1/s) is the conductance of
materials between the source and the model domain (conductance to flow in the
semi-pervious layer adjacent to the boundary). Typically Rb = K'/B', where K' is the
hydraulic conductivity (SI unit: m/s) of the layer and B' (SI unit: m) is its thickness.
Using logical relationships, it is possible to activate these expressions at different times
or under various flow conditions.

When the pressure head Hp is specified instead of the pressure, the boundary condition
is the following:

n ⋅ ρK∇ ( H p + D ) = ρR b [ ( H pb – H p ) + ( D b – D ) ] (6-12)

Hpb is the pressure head (SI unit: m) at the edge of the layer.

THE DARCY’S LAW INTERFACE | 331

 When the hydraulic head H is specified instead of the pressure head, the boundary
condition becomes:

n ⋅ ρK∇H = ρR b [ H b – H ] (6-13)

Hb is the hydraulic head (SI unit: m) at the edge of the layer.

K in Equation 6-12 and Equation 6-13 is the hydraulic conductivity.

At a free surface, such as a water table or seepage face, the pressure is atmospheric (here
taken to be zero), so the total hydraulic potential equals gravitational potential, which
is defined on D.

Gravity effects are not active by default. Select the check box Include
gravity to activate the acceleration of gravity. Setting the elevation D to
zero also turns off gravity effects.

PERVIOUS LAYER
Specify the material properties whether to specify an external pressure, pressure head,
or hydraulic head.

Select an External variable to specify — Pressure and elevation to specify the external
pressure, Pressure head and elevation to specify the external pressure head, or Hydraulic
head. For all selections, enter a value for the Conductance Rb (SI unit: 1/s).

• For Pressure and elevation enter an External pressure pb (SI unit: Pa) and External
elevation Db (SI unit: m).
• For Pressure head and elevation enter an External pressure head Hpb (SI unit: m), Hpb
(SI unit: m) and External elevation Db (SI unit: m).
• For Hydraulic head enter the Hydraulic head Hb (SI unit: m).

Well
The Well feature is intended to model injection or production wells and is available
with the Subsurface Flow Module.

WELL
Enter a value or expression for the Well diameter dw (SI unit: m, the default is 0.1 m).
Select the Well type from the list, Production or Injection well.

332 | CHAPTER 6: FLUID FLOW INTERFACES

Specify either the Pressure (SI unit: Pa), Pressure head (SI unit: m), Hydraulic head (SI
unit: m), or the Mass flow. If you select Mass flow, specify the total Mass flow rate (SI
unit: kg/s), the Mass flow rate per unit length (SI unit: kg/(m·s)) or the Mass flux (SI
unit: kg/(m2·s)).

Fracture Flow
The Fracture Flow node adds fracture flow on boundaries using tangential derivatives
to define the flow along interior boundaries representing fractures within a porous
medium. It is implemented through . Additional subnodes are available from the
context menu (right-click the parent node) or from the Physics toolbar, Attributes
menu.

This feature requires a specific license. For a detailed overview of the functionality
available in each product visit [Link]

THE DARCY’S LAW INTERFACE | 333

 The Free and Porous Media Flow
Interface
The Free and Porous Media Flow (fp) interface ( ) is found under the Porous Media
and Subsurface Flow branch ( ) when adding a physics interface. It 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 Porous Medium 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
Weakly compressible flow from the Compressibility list, to account for small variations in

334 | CHAPTER 6: FLUID FLOW INTERFACES

the density, which are only dependent on the temperature (nonisothermal flow) or
Compressible flow (Ma<0.3) for fully compressible flow. However, for the flow modeled
with this physics interface, the Mach number must be below 0.3.

Swirl Flow
For 2D axisymmetric components, select the Swirl flow check box to include the swirl
velocity component, that is the velocity component u ϕ in the azimuthal direction.
While u ϕ can be nonzero, there can be no gradients in the ϕ direction. Note that this
feature is only available for specific modules. Visit [Link]
products/specifications/ for a detailed overview.

Neglect Inertial Term

Select the Neglect inertial term (Stokes flow) check box if the inertial forces are small
compared to the viscous forces.

Enable porous media domains

The Enable porous media domains check box is selected by default to solve the
Brinkman equations in porous domains. If it is unchecked, the Porous Medium node is
no longer available in this interface.

Include Gravity
Gravity is not included by default. Select the Include gravity check box to activate the
acceleration of gravity. This automatically adds a global Gravity feature node to the
interface model tree, and the buoyancy force is included in the Equations.

Also, when the Include gravity check box is selected, the Use reduced pressure option
changes the pressure formulation from using the total pressure (default) to using the
reduced pressure. This option is suitable for configurations where the density changes
are very small; otherwise, the default formulation can be used. For more information,
see Gravity.

Porous Treatment of No Slip Condition

Choose how the No Slip condition on internal boundaries should be treated. The
options are Standard no slip formulation (default) and Porous slip. The latter option
provides a unified treatment when the porous matrix is fully resolved as well as when
it is under resolved ensuring a smooth transition between regions with different
resolutions; see No Slip under Wall in the The Laminar Flow and Creeping Flow
Interfaces section.

Reference Pressure Level

Enter a Reference pressure level pref (SI unit: Pa). The default value is 1[atm].

THE FREE AND POROUS MEDIA FLOW INTERFACE | 335

 Reference Temperature
Enter a Reference temperature Tref (SI unit: K). The default value is 293.15[K].

Reference Position
If Include gravity is selected, a Reference position rref (SI unit: m) can be specified which
is then used for the calculation of the hydrostatic pressure.

TURBULENCE
Turbulent flow can be simulated by changing the Turbulence model type to RANS
(Reynolds-Averaged Navier–Stokes) or Large Eddy Simulation (which is only available
in 3D). If turbulent flow is activated, you can choose from different Turbulence models
and options for Wall treatment. For a description of the different turbulence models,
wall treatment options, and turbulence model parameters see Theory for the
Turbulent Flow Interfaces in the CFD Module User’s Guide.

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.

336 | CHAPTER 6: FLUID FLOW INTERFACES

 • Electrode-Electrolyte Interface • Porous Medium
Coupling • Mass Source
• Fluid Properties • Volume Force
• Gravity • Wall
• Initial Values
• Porous Electrode Coupling

Note that some features are only available with certain COMSOL products (see
[Link]

The following nodes (listed in alphabetical order) are described for the Laminar Flow
interface in 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 2-4 for links
to common sections and Table 2-5 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.

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 FREE AND POROUS MEDIA FLOW INTERFACE | 337

 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.

Porous Medium
The Porous Medium node adds the Brinkman equations (excluding any mass sources)
to the interface. It has two default subfeatures — the Fluid subfeature where the fluid
density ρ(SI unit: kg/m3) and dynamic viscosity μ (SI unit: Pa·s) are defined and the
Porous Matrix subfeature where the permeability κ (SI unit: m2) and porosity εp
(dimensionless) are specified.

FLOW MODEL
Define if the flow follows a linear or nonlinear pressure-velocity relationship.

• Darcian flow (default) defines a linear relationship.

• Non-Darcian flow defines a nonlinear relationship due to turbulence or inertial
effects.

Fluid
This node defines the material properties of the fluid of the Porous Medium parent
node.

MODEL INPUT
This section contains fields and values that are inputs for expressions defining material
properties. If such user-defined property groups are added, the model inputs appear
here.

FLUID PROPERTIES
Specify the Density ρ and the Dynamic viscosity μ (SI unit: Pa·s) of the fluid. The
defaults use values From material, for User defined enter a value or expression.

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.

338 | CHAPTER 6: FLUID FLOW INTERFACES

Porous Matrix
This node defines the porosity and material properties of the solid matrix of the Porous
Medium parent node.

MODEL INPUT
This section contains fields and values that are inputs for expressions defining material
properties. If such user-defined property groups are added, the model inputs appear
here.

MATRIX PROPERTIES
The Porosity εp (a dimensionless number between 0 and 1) uses by default the value
From material. For User defined the default value is 1 which is equivalent to free flow.

Select a Permeability model to specify the capacity of the porous material to transmit
flow. Depending on the Flow model selection in the parent Porous Medium feature node
you can choose between the following options:

• Permeability (the default) to directly enter the permeability of the porous matrix or
Kozeny-Carman to define the permeability from the porosity and mean Particle
diameter for Darcian flow or
• Forchheimer or Ergun for Non-Darcian flow.

Note that some of these options are only available for certain modules. For a detailed
overview of the functionality available in each product, visit https://
[Link]/products/specifications/.

The default Permeability κ (SI unit: m2) uses the value From material, as defined by the
Porous material list. For User defined select Isotropic to define a scalar value or Diagonal,
Symmetric, or Full 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.

In case a Non-Darcian flow model is chosen in the parent node, Forchheimer is the
default selection for the Permeability model. For Forchheimer, the default Permeability
κ (SI unit: m2) uses the value From material. Furthermore, the dimensionless
Forchheimer parameter cF can be defined. The default value is 0.55.

THE FREE AND POROUS MEDIA FLOW INTERFACE | 339

 If Ergun is selected, enter the mean Particle diameter dp (default value: 0.5 mm). The
permeability κ is then calculated using Equation 2-4 in the Porous Media Flow
Module User’s Guide.

• About Darcian and Non-Darcian Flow in the Porous Media Flow

Module User’s Guide
• Permeability Models in the Porous Media Flow Module User’s Guide

Mass Source
Enter a value or expression for an optional mass source (or sink) Source term Qm (SI
unit: kg/(m3·s)). This term accounts for mass deposit or mass creation within porous
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 a Fluid Properties or Porous
Medium node is active on the domain. It then acts on each fluid element in the
specified domains.

VOLUME FORCE
Enter the components of the Volume force F (SI unit: N/m3).

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.

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.

340 | CHAPTER 6: FLUID FLOW INTERFACES

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.

Gravity
The Gravity global feature is automatically added when Include gravity is selected at the
interface level in the Physical Model settings. It defines the gravity forces from the
Acceleration of gravity value. When a turbulence model that solves for the turbulent
kinetic energy, k, is used, the option Include buoyancy-induced turbulence is available.
When selected, the Buoyancy contribution is by default set to Automatic from
multiphysics. Contributions are only obtained from multiphysics couplings that
support buoyancy-induced turbulence, such as Nonisothermal Flow. If the Buoyancy
contribution is switched to User defined, a text field for the Turbulent Schmidt number
appears. See also Theory for Buoyancy-Induced Turbulence in the CFD Module
User’s Guide.

This feature requires a specific license. For a detailed overview of the functionality
available in each product visit [Link]

ACCELERATION OF GRAVITY
The Acceleration of gravity (SI unit m/s, default value −gconstez in 2D axial symmetry
and 3D and −gconstey in 2D) is used to define the gravity forces. It should be a global
quantity.

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 FREE AND POROUS MEDIA FLOW INTERFACE | 341

 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.

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.

342 | CHAPTER 6: FLUID FLOW INTERFACES

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

THE FREE AND POROUS MEDIA FLOW INTERFACE | 343

 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 Porous Medium feature, which adds the Brinkman equations and
provides interfaces 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 — Porous Medium, 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 2-4 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.

SETTINGS
The Label is the default physics interface name.

344 | CHAPTER 6: FLUID FLOW INTERFACES

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, from the
Compressibility list select Weakly compressible flow which should be used when the
pressure dependency of the density can be neglected, or Compressible flow (Ma<0.3) to
solve for the full compressible flow of which, however, the Mach number must be
below 0.3.

Swirl Flow
For 2D axisymmetric models, select the Swirl flow check box to include the swirl
velocity component, that is the velocity component u ϕ in the azimuthal direction.
While u ϕ can be nonzero, there can be no gradients in the ϕ direction.

Note that this feature is only available for specific modules. See https://
[Link]/products/specifications/ for a detailed overview.

Neglect Inertial Term (Stokes–Brinkman Flow)

The Neglect inertial term (Stokes–Brinkman) check box is selected by default to model
flow at low Reynolds numbers for which the inertial term can be neglected. This results
in the linear Stokes–Brinkman equations.

Include Gravity
Gravity is not included by default. Select the Include gravity check box to activate the
acceleration of gravity. This automatically adds a global Gravity feature node to the
interface model tree, and the buoyancy force is included in the Equations.

Also, when the Include gravity check box is selected, the Use reduced pressure option
changes the pressure formulation from using the total pressure (default) to using the
reduced pressure. This option is suitable for configurations where the density changes

THE BRINKMAN EQUATIONS INTERFACE | 345

 are very small; otherwise, the default formulation can be used. For more information,
see Gravity.

Porous Treatment of No Slip Condition

Choose how the No Slip condition on Wall boundaries and Interior Wall boundaries
adjacent to Porous Medium should be treated. The options are Standard no slip
formulation (default) and Porous slip. The latter option provides a unified treatment
when the porous matrix is fully resolved as well as when it is under resolved ensuring
a smooth transition between regions with different resolutions; see No Slip under Wall
in the The Laminar Flow and Creeping Flow Interfaces section.

Reference Pressure Level

Enter a Reference pressure level pref (SI unit: Pa). The default value is 1[atm].

Reference Temperature Level

Enter a Reference temperature level Tref (SI unit: K). The default value is 293.15[K].

Reference Position
If Include gravity is selected, a Reference position rref (SI unit: m) can be specified which
is then used for the calculation of the hydrostatic pressure.

TURBULENCE
Turbulent flow can be simulated by changing the Turbulence model type to RANS
(Reynolds-Averaged Navier–Stokes). If turbulent flow is activated, one of the
following Turbulence models can be chosen: Algebraic yPlus, L-VEL, and k-ε, and Wall
functions are preset for Wall treatment. For more information about turbulence
modeling, see Theory for the Turbulent Flow Interfaces in the CFD Module User’s
Guide.

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 More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box. Normally these settings do not
need to be changed.

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

346 | CHAPTER 6: FLUID FLOW INTERFACES

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:

• Porous Medium • Volume Force

• Initial Values • Fluid Properties
• Mass Source

THE BRINKMAN EQUATIONS INTERFACE | 347

 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

• Inlet • Point Mass Source
• Line Mass Source • Pressure Point Constraint
• Boundary Stress • Symmetry
• Outlet • Wall
• Open Boundary

In the COMSOL Multiphysics Reference Manual see Table 2-4 for links
to common sections and Table 2-5 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.

Porous Medium
The Porous Medium node adds the Brinkman equations: Equation 4-25 and
Equation 4-26 (excluding any mass sources). It has two default subfeatures — the
Fluid subfeature where the fluid density ρ(SI unit: kg/m3) and dynamic viscosity μ (SI
unit: Pa·s) are defined and the Porous Matrix subfeature where the permeability κ (SI
unit: m2) and porosity εp (dimensionless) are specified.

FLOW MODEL
Define if the flow follows a linear or nonlinear pressure-velocity relationship.

• Darcian flow (default) defines a linear relationship.

• Non-Darcian flow defines a nonlinear relationship due to turbulence or inertial
effects.

Fluid
This node defines the material properties of the fluid of the Porous Medium parent
node.

348 | CHAPTER 6: FLUID FLOW INTERFACES

MODEL INPUT
This section contains fields and values that are inputs for expressions defining material
properties. If such user-defined property groups are added, the model inputs appear
here.

FLUID PROPERTIES
Specify the Density ρ and the Dynamic viscosity μ (SI unit: Pa·s) of the fluid. The
defaults use values From material, for User defined enter a value or expression.

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.

Porous Matrix
This node defines the porosity and material properties of the solid matrix of the Porous
Medium parent node.

MODEL INPUT
This section contains fields and values that are inputs for expressions defining material
properties. If such user-defined property groups are added, the model inputs appear
here.

MATRIX PROPERTIES
The Porosity εp (a dimensionless number between 0 and 1) uses by default the value
From material. For User defined the default value is 1.

Select a Permeability model to specify the capacity of the porous material to transmit
flow. Depending on the Flow model selection in the parent Porous Medium feature node
you can choose between the following options:

• Permeability (the default) to directly enter the permeability of the porous matrix or
Kozeny-Carman to define the permeability from the porosity and mean Particle
diameter for Darcian flow or
• Forchheimer or Ergun for Non-Darcian flow.

Note that some of these options are only available for certain modules. For a detailed
overview of the functionality available in each product, visit https://
[Link]/products/specifications/.

THE BRINKMAN EQUATIONS INTERFACE | 349

 The default Permeability κ (SI unit: m2) uses the value From material, as defined by the
Porous material list. For User defined select Isotropic to define a scalar value or Diagonal,
Symmetric, or Full 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.

In case a Non-Darcian flow model is chosen in the parent node, Forchheimer is the
default selection for the Permeability model. For Forchheimer, the default Permeability
κ (SI unit: m2) uses the value From material. Furthermore, the dimensionless
Forchheimer parameter cF can be defined. The default value is 0.55.

If Ergun is selected, enter the mean Particle diameter dp (default value: 0.5 mm). The
permeability κ is then calculated using Equation 2-4 in the Porous Media Flow
Module User’s Guide.

• About Darcian and Non-Darcian Flow in the Porous Media Flow

Module User’s Guide
• Permeability Models in the Porous Media Flow Module User’s Guide

Mass Source
The Mass Source node adds a mass source (or mass sink) Qm to the right-hand side of
the continuity equation: Equation 6-48. 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 m (6-14)
∂t p

DOMAIN SELECTION
Only Porous Matrix domains are available.

MASS SOURCE
Enter a value or expression for the Source term Qbr (SI unit: kg/(m3·s)). The default
is 0 kg/(m3·s).

350 | CHAPTER 6: FLUID FLOW INTERFACES

Volume Force
Use the Volume Force node to specify the force F on the right-hand side of
Equation 6-49. It then acts on each fluid element in the specified domains.

ρ-  ∂u u
---- + ( u ⋅ ∇ ) ----- =
εp  ∂ t εp
(6-15)
1 T 2   –1 Q m
– ∇ p + ∇ ⋅ -----  μ ( ∇u + ( ∇u ) ) – --- μ ( ∇ ⋅ u )I  –  κ μ + -------
- u + F
εp  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.

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

THE BRINKMAN EQUATIONS INTERFACE | 351

 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.

Gravity
The Gravity global feature is automatically added when Include gravity is selected at the
interface level in the Physical Model settings. It defines the gravity forces from the
Acceleration of gravity value. When a turbulence model that solves for the turbulent

352 | CHAPTER 6: FLUID FLOW INTERFACES

kinetic energy, k, is used, the option Include buoyancy-induced turbulence is available.
When selected, the Buoyancy contribution is by default set to Automatic from
multiphysics. Contributions are only obtained from multiphysics couplings that
support buoyancy-induced turbulence, such as Nonisothermal Flow. If the Buoyancy
contribution is switched to User defined, a text field for the Turbulent Schmidt number
appears. See also Theory for Buoyancy-Induced Turbulence in the CFD Module
User’s Guide.

This feature requires a specific license. For a detailed overview of the functionality
available in each product visit [Link]

ACCELERATION OF GRAVITY
The Acceleration of gravity (SI unit m/s, default value −gconstez in 2D axial symmetry
and 3D and −gconstey in 2D) is used to define the gravity forces. It should be a global
quantity.

THE BRINKMAN EQUATIONS INTERFACE | 353

 Theory for the Laminar Flow and
Creeping Flow Interfaces
The theory for the Single-Phase Flow, Laminar Flow interface is described in this
section:

• General Single-Phase Flow Theory

• Compressible Flow
• Weakly Compressible Flow
• The Mach Number Limit
• Incompressible Flow
• The Reynolds Number
• Gravity
• Theory for the Wall Boundary Condition
• Prescribing Inlet and Outlet Conditions
• Fully Developed Flow (Inlet)
• Fully Developed Flow (Outlet)
• No Viscous Stress
• Normal Stress Boundary Condition
• Mass Sources for Fluid Flow
• Numerical Stability — Stabilization Techniques for Fluid Flow
• Solvers for Laminar Flow
• Pseudo Time Stepping for Laminar Flow Models
• Discontinuous Galerkin Formulation
• Particle Tracing in Fluid Flow
• References for the Single-Phase Flow, Laminar Flow Interfaces

The theory about most boundary conditions is found in Ref. 2.

354 | CHAPTER 6: FLUID FLOW INTERFACES

General Single-Phase Flow Theory
The Single-Phase Fluid Flow interfaces are based on the Navier–Stokes equations,
which in their most general form read

∂ρ
------ + ∇ ⋅ ( ρu ) = 0 (6-16)
∂t

∂u
ρ ------ + ρ ( u ⋅ ∇ )u = ∇ ⋅ [ – pI + K ] + F (6-17)
∂t

∂T T ∂ρ ∂p
ρC p  ------- + ( u ⋅ ∇ )T = – ( ∇ ⋅ q ) + K:S – ---- -------  ------ + ( u ⋅ ∇ )p + Q (6-18)
 ∂t  ρ ∂T p  ∂t 

where

• ρ is the density (SI unit: kg/m3)

• u is the velocity vector (SI unit: m/s)
• p is pressure (SI unit: Pa)
• I is the identity matrix (unitless)
• K is the viscous stress tensor (SI unit: Pa)
• F is the volume force vector (SI unit: N/m3)
• Cp is the specific heat capacity at constant pressure (SI unit: J/(kg·K))
• T is the absolute temperature (SI unit: K)
• q is the heat flux vector (SI unit: W/m2)
• Q contains the heat sources (SI unit: W/m3)
• S is the strain-rate tensor:

1
S = --- ( ∇u + ( ∇u ) T )
2

The operation “:” denotes a contraction between tensors defined by

a:b =   anm bnm (6-19)

n m

This is sometimes referred to as the double dot product.

Equation 6-16 is the continuity equation and represents conservation of mass.

Equation 6-17 is a vector equation which represents conservation of momentum.

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 355
 Equation 6-18 describes the conservation of energy, formulated in terms of
temperature. This is an intuitive formulation that facilitates boundary condition
specifications.

To close the equation system, Equation 6-16 through Equation 6-18, constitutive
relations are needed.

For a Newtonian fluid, which has a linear relationship between stress and strain, Stokes
(Ref. 1) deduced the following expression:

2
K = 2μS – --- μ ( ∇ ⋅ u )I (6-20)
3

The dynamic viscosity, μ (SI unit: Pa·s), for a Newtonian fluid is allowed to depend on
the thermodynamic state but not on the velocity field. All gases and many liquids can
be considered Newtonian.

For an inelastic non-Newtonian fluid, the relationship between stress and strain rate is
nonlinear, and an apparent viscosity is introduced instead of the dynamic viscosity.
Examples of non-Newtonian fluids are honey, mud, blood, liquid metals, and most
polymer solutions.

In theory, the same equations describe both laminar and turbulent flows. In practice,
however, the mesh resolution required to simulate turbulence with the Laminar Flow
interface makes such an approach impractical.

There are several books where derivations of the Navier–Stokes equations

and detailed explanations of concepts such as Newtonian fluids can be
found. See, for example, the classical text by Batchelor (Ref. 3) and the
more recent work by Panton (Ref. 4).

Many applications describe isothermal flows for which Equation 6-18 is decoupled
from Equation 6-16 and Equation 6-17.

2D AXISYMMETRIC FORMULATIONS
A 2D axisymmetric formulation of Equation 6-16 and Equation 6-17 requires ∂ ⁄ ∂φ
to be zero. That is, there must be no gradients in the azimuthal direction. A common
additional assumption is, however, that u φ = 0 . In such cases, the φ -equation can be
removed from Equation 6-17. The resulting system of equations is both easier to
converge and computationally less expensive compared to retaining the φ -equation.

356 | CHAPTER 6: FLUID FLOW INTERFACES

The default 2D axisymmetric formulation of Equation 6-16 and Equation 6-17
therefore assumes that

∂ ⁄ ∂φ = 0
uφ = 0

Compressible Flow
The equations of motion for a single-phase fluid are the continuity equation:

∂ρ
------ + ∇ ⋅ ( ρu ) = 0 (6-21)
∂t

and the momentum equation:

∂u
ρ ------ + ρu ⋅ ∇u = – ∇p + ∇ ⋅  μ ( ∇u + ( ∇u ) T ) – --- μ ( ∇ ⋅ u )I + F
2
(6-22)
∂t  3 

These equations are applicable for incompressible as well as for compressible flow with
density and viscosity variations.

Weakly Compressible Flow

The same equations as for Compressible Flow are applied for weakly compressible flow.
The only difference is that the density is evaluated at the reference pressure. The
density may be a function of other quantities, in particular it may be temperature
dependent.

The weakly compressible flow equations are valid for incompressible as well as
compressible flow with density variations independent of the pressure.

Provided that the densities dependency pressure is specified through model inputs, the
density is automatically evaluated at the reference pressure level.

The Mach Number Limit

An important dimensionless number in fluid dynamics is the Mach number, Ma,
defined by

u
Ma = ------
a

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 357
 where a is the speed of sound. A flow is formally incompressible when Ma = 0. This is
theoretically achieved by letting the speed of sound tend to infinity. The Navier–Stokes
equations then have the mathematical property that pressure disturbances are
instantaneously propagated throughout the entire domain. This results in a parabolic
equation system.

The momentum equation, Equation 6-22, is parabolic for unsteady flow and elliptic
for steady flow, whereas the continuity equation, Equation 6-21, is hyperbolic for both
steady and unsteady flow. The combined system of equations is thus hybrid
parabolic-hyperbolic for unsteady flow and hybrid elliptic-hyperbolic for steady flow.
An exception occurs when the viscous term in Equation 6-22 becomes vanishingly
small, such as at an outflow boundary, in which case the momentum equation becomes
locally hyperbolic. The number of boundary conditions to apply on the boundary then
depends on the number of characteristics propagating into the computational domain.
For the purely hyperbolic system, the number of characteristics propagating from the
boundary into the domain changes as the Mach number passes through unity. Hence,
the number of boundary conditions required to obtain a numerically well-posed
system must also change. The compressible formulation of the laminar and turbulent
interfaces uses the same boundary conditions as the incompressible formulation, which
implies that the compressible interfaces are not suitable for flows with a Mach number
larger than or equal to one. Yet, the practical Mach number limit is lower than one.
The main reason is that the numerical scheme (stabilization and boundary conditions)
of the Laminar Flow interface does not recognize the direction and speed of pressure
waves. The fully compressible Navier–Stokes equations do, for example, start to display
very sharp gradients already at moderate Mach numbers. But the stabilization for the
single-phase flow interface does not necessarily capture these gradients. It is impossible
to give an exact limit where the low Mach number regime ends and the moderate
Mach number regime begins, but a rule of thumb is that the Mach number effects start
to appear at Ma = 0.3. For this reason, the compressible formulation is referred to as
Compressible flow (Ma<0.3) in COMSOL Multiphysics.

Incompressible Flow
When the temperature variations in the flow are small, a single-phase fluid can often
be assumed incompressible; that is, ρ is constant or nearly constant. This is the case for
all liquids under normal conditions and also for gases at low velocities. For constant ρ,
Equation 6-21 reduces to

ρ∇ ⋅ u = 0 (6-23)

358 | CHAPTER 6: FLUID FLOW INTERFACES

and Equation 6-22 becomes

∂u T
ρ + ρ ( u ⋅ ∇ )u = ∇ ⋅ [ – pI + μ ( ∇u + ( ∇u ) ) ] + F (6-24)
∂t

Provided that the densities dependency on temperature and pressure is specified

through model inputs, the density is evaluated at the reference pressure level and at the
reference temperature. However, if the density is a function of other quantities such as
a concentration field, or if the density is specified by a user defined expression, the user
has to make sure that the density is defined as constant when the incompressible flow
formulation is used.

The Reynolds Number

A fundamental characteristic in analyses of fluid flow is the Reynolds number:

ρUL
Re = ------------
μ

where U denotes a velocity scale, and L denotes a representative length. The Reynolds
number represents the ratio between inertial and viscous forces. At low Reynolds
numbers, viscous forces dominate and tend to damp out all disturbances, which leads
to laminar flow. At high Reynolds numbers, the damping in the system is very low,
giving small disturbances the possibility to grow by nonlinear interactions. If the
Reynolds number is high enough, the flow field eventually ends up in a chaotic state
called turbulence.

Note that the Reynolds number can have different meanings depending on the length
scale and velocity scale. To be able to compare two Reynolds numbers, they must be
based on equivalent length and velocity scales.

The Fluid Flow interfaces automatically calculate the local cell Reynolds number
Rec = ρ|u|h/(2μ) using the element length h for L and the magnitude of the velocity
vector u for the velocity scale U. This Reynolds number is not related to the character
of the flow field, but to the stability of the numerical discretization. The risk for
numerical oscillations in the solution increases as Rec grows. The cell Reynolds
number is a predefined quantity available for visualization and evaluation (typically it
is available as: [Link]).

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 359
 Gravity

DEFINITION
The gravity force is defined from the acceleration of gravity vector, g, and the density,
ρ. Under usual conditions and in Cartesian coordinates with the z-axis in the vertical
direction,

 0 
 
g =  0 .
 
 – g const 

When gravity is considered, a volume force equal to ρg is included in the momentum

equation. For example, for laminar weakly compressible flow, it reads:

∂u
ρ ------ + ρu ⋅ ∇u = ∇ ⋅  – pI + μ ( ∇u + ( ∇u ) T ) – --- μ ( ∇ ⋅ u )I + F + ρg
2
(6-25)
∂t 3

Introducing a constant reference density ρref, and assuming that g is homogeneous,

this equation is equivalently written:

∂u
ρ ------ + ρu ⋅ ∇u=
∂t
(6-26)
∇ ⋅  – pI + μ ( ∇u + ( ∇u ) T ) – --- μ ( ∇ ⋅ u )I + ρ ref g ⋅ ( r – r ref ) + F + ( ρ – ρ ref )g
2
3

where r is the position vector and rref is an arbitrary reference position vector.

From this equation, it is convenient to define the reduced pressure which accounts for
the hydrostatic pressure, p˜ = p – ρ ref g ⋅ ( r – r ref )

∂u
ρ ------ + ρu ⋅ ∇u = ∇ ⋅  – p˜ I + μ ( ∇u + ( ∇u ) T ) – --- μ ( ∇ ⋅ u )I +
2
∂t  3  (6-27)
F + ( ρ – ρ ref )g

In Equation 6-27, the gravity force is written ( ρ – ρ ref )g .

PRESSURE FORMULATION
When the relative pressure is used (default option) the interface dependent variable
represents the relative pressure and the absolute pressure is defined as p A = p ref + p .
When the pressure is used to define a boundary condition (for example when p0

360 | CHAPTER 6: FLUID FLOW INTERFACES

defines the pressure condition at an outlet), it represents the relative pressure. Hence
defining the outlet pressure as p hydro, approx = – ρ ref g ⋅ ( r – r ref ) compensates for the
gravity force for an ambient reference pressure of 0 Pa when the density is constant,
there is no external force, and provided pref, g and r0 are defined consistently.

When the reduced pressure is used, the interface dependent variable (named p by
default) represents the reduced pressure. The absolute pressure is then defined as
p A = p ref – ρ ref g ⋅ ( r – r ref ) + p . In this case when the pressure is used to define a
boundary condition (for example to define a pressure condition at an outlet), its value
corresponds to the reduced pressure. Hence, the prescribed pressure compensates for
an approximate hydrostatic pressure, p hydro, approx = – ρ ref g ⋅ ( r – r ref ) which is exact
only when the density is constant and there is no external force.

PRESSURE BOUNDARY CONDITION

For an immobile fluid the momentum equation simplifies to ∇ ⋅ ( pI ) = F + ρg or

∇ ⋅ ( – p˜ I ) = F + ( ρ – ρ ref )g depending on the pressure formulation.

For incompressible flow, assuming there are no external forces, this leads respectively
to p = – ρ ref g ⋅ ( r – r ref ) + p 0 or p˜ = p 0 .

Theory for the Wall Boundary Condition

See Wall for the node settings.

SLIP
The Slip condition assumes that there are no viscous effects at the slip wall and hence,
no boundary layer develops. From a modeling point of view, this is a reasonable
approximation if the important effect of the wall is to prevent fluid from leaving the
domain. Mathematically, the constraint can be formulated as:

u ⋅ n = 0, ( – pI + μ ( ∇u + ( ∇u ) T ) )n = 0

The no-penetration term takes precedence over the Neumann part of the condition
and the above expression is therefore equivalent to

u ⋅ n = 0, K n – ( K n ⋅ n )n = 0
K n = μ ( ∇u + ( ∇u ) T )n

expressing that there is no flow across the boundary and no viscous stress in the
tangential direction.

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 361
 For a moving wall with translational velocity utr, u in the above equations is replaced
by the relative velocity urel = u−utr.

POROUS SLIP
The Porous slip option, which can be chosen in the Porous treatment of no slip condition
list when Enable porous media domains is activated, results in special treatment of Wall
boundaries and Interior Wall boundaries adjacent to porous domains (Porous Medium
feature). Namely, similar to the Navier slip boundary condition, no penetration and
tangential stress conditions are applied at the wall:

μ u slip
u ⋅ n = 0, K n – ( K n ⋅ n )n = – ----- ---------- ,
ε p y ps
μ T
u slip = u – ( u ⋅ n )n , K n = ----- ( ∇u + ( ∇u ) )n
εp

Here, K n is the viscous wall traction, n is the wall normal, u slip is the tangential
velocity at the wall while the real no slip is assumed to be at a distance d w (half-height
of the first cell adjacent to the wall) outside the wall, and y ps is the porous slip length.
An analytical derivation of the velocity profile in the boundary layer where the pressure
gradient is balanced by the sum of the Darcy term, Forchheimer drag, and a viscous
term (neglecting convective terms) leads to the following expression for y ps :

 1 + X e – ξp  1 + X e – ξp 2 d l pore

ξ
= l̃  --------------------------  -------------------------- e p – 1 ,
p p w
y ps

ξ p = ------ , l̃ = ------------------------,
–ξ p  1 + X p  l̃ 1 + 2c β
 1 – Xp e 

4
1 + 2c β – 1 + --- c β 1 + 4c D – 1 β ND κ 2
3
X p = --------------------------------------------------- , c β = -------------------------------- , c D = ----------- ------ ∇p - ρg
2 μ μ
1 + 2c β + 1 + 4--- c β
3

where l pore = κ ⁄ ε p is the porous length scale, β ND = ρc F ⁄ κ is the non-Darcian

coefficient ( c F is the Forchheimer coefficient), g is the gravity vector, and
ξ p ,˜l ,X p ,c β ,c D are intermediate variables. This formula is used when the
Pressure-gradient formulation is chosen and it reads pressure-gradient at the wall. By
default, the Velocity formulation is activated and the corresponding formula is:

362 | CHAPTER 6: FLUID FLOW INTERFACES

 ξ w d l pore
y ps = l̃ ( e p – 1 ) , ξ p = ------ , l̃ = ------------------------,
l̃ 1 + 2c β
β ND κ u slip l pore 2 1⁄3
c β =  ---------------------------- ----------  ⁄ 2
 μ dw 

Although this formulation is an approximation, since it uses slip velocity at the wall to
reconstruct the pressure gradient, it is rather accurate. Moreover, the influence of
convective terms is partially accounted for in this formulation.

SLIDING WALL
The sliding wall option is appropriate if the wall behaves like a conveyor belt; that is,
the surface is sliding in its tangential direction. The wall does not have to actually move
in the coordinate system.

• In 2D, the tangential direction is unambiguously defined by the direction of the

boundary, but the situation becomes more complicated in 3D. For this reason, this
boundary condition has slightly different definitions in the different space
dimensions.
• For 2D and 2D axisymmetric components, the velocity is given as a scalar Uw and
the condition prescribes
u ⋅ n = 0, u ⋅ t = Uw

where t = (ny , −nx) for 2D and t = (nz, −nr) for axial symmetry.
• For 3D components, the velocity is set equal to a given vector uw projected onto
the boundary plane:
u w – ( n ⋅ u w )n
u = ---------------------------------------- u w
u w – ( n ⋅ u w )n

The normalization makes u have the same magnitude as uw even if uw is not exactly
parallel to the wall.

Navier Slip
This boundary condition enforces no-penetration at the wall, u ⋅ n wall = 0 , and adds
a tangential stress

μ
K nt = – --- u slip
β

where K nt = K n – ( K n ⋅ n wall )n wall , K n = Kn wall and K is the viscous stress tensor.

β is a slip length, and u slip = u – ( u ⋅ n wall )n wall is the velocity tangential to the wall.

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 363
 The boundary condition does not set the tangential velocity component to zero;
however, the extrapolated tangential velocity component is 0 at a distance β outside
the wall.

The Slip Length setting is per default set to Factor of minimum element length. The slip
length β is then defined as β = f h h min , where h min is the smallest element side
(corresponds to the element size in the wall normal direction for boundary layer
elements) and f h is a user input.

In cases where the wall movement is nonzero, Account for the translational wall velocity
in the friction force may be selected to use ( u – u bnd – ( ( u – u bnd ) ⋅ n wall )n wall )
instead of u slip in the friction force. Then, the extrapolated tangential velocity
component is u bnd at a distance β outside of the wall. Note that the Velocity of sliding
wall uw is always accounted for in the friction force.

The Navier Slip option is not available when selecting a turbulence model.

CONSTRAINT SETTINGS
The wall feature uses three different techniques to constraint the velocity field:

• Pointwise constraints is the standard technique to enforce strong constraints in the

finite element method. The desired value of the velocity is prescribed at each node
point in the mesh. Since the constraint is enforced locally at each node, only local
values are affected by the constraint and the constraints are independent of each
other. The solvers can therefore eliminate both the constrained degrees of freedom
and the constraint force terms, effectively reducing the number of degrees of
freedom being solved for.
The main advantage of pointwise constraints is that they enforce the constraint
exactly pointwise. This means that they do not introduce any leakage of the velocity
across the wall, unless specified. The main disadvantage of pointwise constraints is
that they introduce locking effects when trying to impose a no-penetration
condition for the velocity, u · n = 0, on curved walls or walls with sharp corners.
• Using Weak constraints is an alternative method to prescribe the velocity. It consists
on enforcing the boundary condition for the velocity via Lagrange multipliers.
Their main advantage is that the Lagrange multiplier can provide an accurate
representation of the reaction flux at the wall. Their main disadvantage is that they
introduce extra unknowns, and are usually difficult to combine with other constraint
methods on adjacent boundaries. Moreover, they may require extra constraints for

364 | CHAPTER 6: FLUID FLOW INTERFACES

 the Lagrange multipliers. For more information, see Weak Constraints in the
COMSOL Multiphysics Reference Manual.
• Discontinuous Galerkin (DG) constraints use a numerical flux to prescribe the
velocity at the wall. They impose the constraint in a integral sense rather than
pointwise, and do not suffer from the locking effects introduced by pointwise
constraints when trying to prescribe a no penetration condition for the velocity.
They are also better behaved when prescribing nonlinear constraints. Their main
disadvantage is that the constraint is only imposed approximately, and may produce
small leaks. For more information, see Discontinuous Galerkin Formulation.

The following combination of Constraint techniques can be selected in the Constraint

Setting sections of Wall boundary conditions:

• Use default settings. The default settings use different constraint methods
depending on whether only the normal component of the velocity is prescribed,
such as in the no penetration condition, u · n = 0, imposed for example in Slip walls
or No Slip walls using Wall Functions or Automatic Wall Treatment, or both
tangential and normal components are prescribed, as is the case of No Slip walls in
laminar flow.
DG constraints are used to impose the no penetration condition for Slip walls. When
a No Slip condition is prescribed, pointwise constraints are used except for moving
walls where DG constraints are used.
• Use Pointwise constraints.
• Use DG constraints.
• Use Weak constraints. Weak constraints are not available on Interior Walls.
• Use Mixed constraints. This option is only available when both the tangential and
normal components of the velocity need to be prescribed. The velocity on the wall
normal direction is imposed via pointwise constraints. The constraint for the
tangential directions is relaxed, and DG constraints are used instead. This provides
improved accuracy and performance when working with coarse boundary layer
meshes. For more information, see Ref. 18.

Prescribing Inlet and Outlet Conditions

The Navier–Stokes equations can show large variations in mathematical behavior,
ranging from almost completely elliptic to almost completely hyperbolic. This has
implications when it comes to prescribing admissible boundary conditions. There is

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 365
 also a discrepancy between mathematically valid boundary conditions and practically
useful boundary conditions. See Inlet and Outlet for the node settings.

INLET CONDITIONS
An inlet requires specification of the velocity components. The most robust way to do
this is to prescribe a velocity field using a Velocity condition.

A common alternative to prescribing the complete velocity field is to prescribe a

pressure and all but one velocity component. The pressure cannot be specified
pointwise because this is mathematically over-constraining. Instead the pressure can be
specified via a stress condition:

∂u n
– p + 2μ --------- = F n (6-28)
∂n

where ∂un/∂n is the normal derivative of the normal velocity component.

Equation 6-28 is prescribed by the Pressure condition in the Inlet and Outlet features
and the Normal stress condition in the Open Boundary and Boundary Stress features.
Equation 6-28 is mathematically more stringent compared to specifying the pressure
pointwise and at the same time cannot guarantee that p obtains the desired value. In
practice, p is close to Fn, except for low Reynolds number flows where viscous effects
are the only effects that balance the pressure. In addition to Equation 6-28, all but one
velocity component must be specified. For low Reynolds numbers, this can be specified
by a vanishing tangential stress condition:

∂u t
μ -------- = 0
∂n

which is what the Normal stress condition does. Vanishing tangential stress becomes a
less well-posed inlet condition as the Reynolds number increases. The Pressure
condition in the Inlet feature therefore requires a flow direction to be prescribed,
which provides a well-posed condition independent of Reynolds number.

OUTLET CONDITIONS
The most common approach is to prescribe a pressure via a normal stress condition on
the outlet. This is often accompanied by a vanishing tangential stress condition:

∂u t
μ -------- = 0
∂n

366 | CHAPTER 6: FLUID FLOW INTERFACES

where ∂ut/∂n is the normal derivative of the tangential velocity field. It is also possible
to prescribe ut to be zero. The latter option should be used with care since it can have
a significant effect on the upstream solution.

The elliptic character of the Navier-Stokes equations mathematically permit specifying

a complete velocity field at an outlet. This can, however, be difficult to apply in
practice. The reason being that it is hard to prescribe the outlet velocity so that it is
consistent with the interior solution at each point. The adjustment to the specified
velocity then occurs across an outlet boundary layer. The thickness of this boundary
layer depends on the Reynolds number; the higher the Reynolds number, the thinner
the boundary layer.

ALTERNATIVE FORMULATIONS
COMSOL provides several specialized boundary conditions that either provide
detailed control over the flow at the boundary or that simulate specific devices. In
practice they often prescribe a velocity or a pressure, but calculate the prescribed values
using for example ODEs.

Normal Stress Boundary Condition

Fully Developed Flow (Inlet)

The Fully developed flow boundary condition can be understood from the following
figure:

pinl Ω

The flow to the domain Ω is assumed to enter through a straight channel of length L.
The channel is a virtual extrusion of the inlet cross section and a pressure constant
pressure Pinl is applied on the inlet of the virtual channel.

The Fully Developed Flow boundary condition prescribes that the tangential flow
component on the boundary is zero:

u – ( u ⋅ n )n = 0

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 367
 The momentum equation for a fully developed flow in the virtual extrusion of the inlet
cross section can then be projected onto the inlet boundary with the following weak
equation as the result:

( – μ ( ∇tu + ( ∇tu ) T ) + ( p + P inl ) ⁄ 2 ) ∇tûL – P inl ( n ⋅ û )

The exact value of L is somewhat arbitrary as long as it is not too high or too low. L is
therefore set to ten times the inlet edge length in 2D and to ten times the square root
of the inlet area in 2D axisymmetry and in 3D.

The fact that the velocity profile is not prescribed, but rather the solution of a projected
weak contribution, means that the actual velocity profile that is obtained on the inlet
can deviate from the analytical fully developed flow profile (in cases such an analytical
solution exists) if required by the solution inside the computational domain, Ω. This is
most notably if the flow is strongly curved just downstream of the inlet. This can for
example be the case if an object is positioned just downstream of the inlet or if the
adjacent boundaries are not orthogonal to the inlet. The analytical solution can in
these cases be recovered by including a little bit of the inlet channel in the
computational domain.

The inlet pressure, Pinl, must be solved for and the its equation is a discrete algebraic
equation (DAE) for Pinl. When, for example, the average velocity is specified, the DAE
reads

(  u ⋅ n + U av )P̂ inl

where <⋅> denotes the average over the inlet. Since the equation for Pinl is a DAE (the
equation for Pinl does not contain Pinl), it must be solved coupled to Navier–Stokes
and it must be treated by a Vanka pre-smoother and post-smoother if iterative solvers
are used.

The boundary conditions for the virtual inlet channel are inherited from the
boundaries adjacent to the inlet channel. Virtual boundaries adjacent to walls (except
slip walls) are treated as no-slip walls. Virtual boundaries adjacent to any other type of
boundary are treated as slip-walls (or equivalently as symmetry boundaries). So in the
figure above, if the lower boundary of Ω is a no-slip wall and the top boundary is a
symmetry boundary, the lower boundary of the virtually extruded channel becomes a
no-slip wall and the upper boundary becomes a symmetry boundary.

Algebraic turbulence models need to additional equations or constraints. For all other
turbulence models, their weak equations in the virtual inlet channel are projected onto

368 | CHAPTER 6: FLUID FLOW INTERFACES

the inlet of the computational domain. The projections are regularized to prevent the
production to fall to zero, so the solutions of the projects can show slight deviation
from the correct solutions close to no-slip walls.

Fully Developed Flow (Outlet)

The Fully developed flow boundary condition can be understood from the following
figure:

Ω pexit

The flow to the domain Ω is assumed to enter through a straight channel of length L.
The channel is a virtual extrusion of the inlet cross section and a pressure constant
pressure Pexit is applied on the inlet of the virtual channel.

The Fully Developed Flow boundary condition prescribes that the tangential flow
component on the boundary is zero:

u – ( u ⋅ n )n = 0

The momentum equation for a fully developed flow in the virtual extrusion of the inlet
cross section can then be projected onto the inlet boundary with the following weak
equation as the result:

( – μ ( ∇tu + ( ∇tu ) T ) + ( p + P exit ) ⁄ 2 ) ∇tûL – P exit ( n ⋅ û )

The exact value of L is somewhat arbitrary as long as it is not too high or too low. L is
therefore set to ten times the inlet edge length in 2D and to ten times the square root
of the inlet area in 2D axisymmetry and in 3D.

The fact that the velocity profile is not prescribed, but rather the solution of a projected
weak contribution, means that the actual velocity profile that is obtained on the outlett
can deviate from the analytical fully developed flow profile (in cases such an analytical
solution exists) if required by the solution inside the computational domain, Ω. The
inlet pressure, Pexit, must be solved for and the its equation is a discrete algebraic
equation (DAE) for Pexit. When, for example, the average velocity is specified, the
DAE reads

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 369
 (  u ⋅ n + U av )P̂ exit

where <⋅> denotes the average over the inlet. Since the equation for Pext is a DAE, it
must be solved coupled to Navier–Stokes and it must be treated by a Vanka
pre-smoother and post-smoother if iterative solvers are used.

The boundary conditions for the virtual outlet channel are inherited from the
boundaries adjacent to the outlet channel. Virtual boundaries adjacent to walls (except
slip walls) are treated as no-slip walls. Virtual boundaries adjacent to any other type of
boundary are treated as slip-walls (or equivalently as symmetry boundaries).

No Viscous Stress
For this module, and in addition to the Pressure, No Viscous Stress boundary
condition, the viscous stress condition sets the viscous stress to zero:

 μ ( ∇u + ( ∇u ) T ) – 2
--- μ ( ∇ ⋅ u )I n = 0
 3 

( μ ( ∇u + ( ∇u ) T ) )n = 0

using the compressible/weakly compressible and the incompressible formulation,

respectively.

The condition is not a sufficient outlet condition since it lacks information about the
outlet pressure. It must hence be combined with pressure point constraints on one or
several points or lines surrounding the outlet.

This boundary condition is numerically the least stable outlet condition, but can still
be beneficial if the outlet pressure is nonconstant due to, for example, a nonlinear
volume force.

Normal Stress Boundary Condition

The total stress on the boundary is set equal to a stress vector of magnitude f0, oriented
in the negative normal direction:

 – pI +  μ ( ∇u + ( ∇u ) T ) – 2
--- μ ( ∇ ⋅ u )I  n = – f 0 n
  3 

( – pI + μ ( ∇u + ( ∇u ) T ) )n = – f 0 n

370 | CHAPTER 6: FLUID FLOW INTERFACES

using the compressible/weakly compressible and the incompressible formulation,
respectively.

This implies that the total stress in the tangential direction is zero. This boundary
condition implicitly sets a constraint on the pressure which for 2D flows is

∂u n
p = 2μ ---------- + f 0 (6-29)
∂n

If ∂un/∂n is small, Equation 6-29 states that p ≈ f0.

The Normal Stress condition is the mathematically correct version of the condition
(Ref. 4), but it is numerically less stable.

Pressure Boundary Condition

For single-phase flow, a mathematically correct natural boundary condition for outlets
is

 – pI + μ ( ∇u + ( ∇u ) T ) – 2
--- μ ( ∇ ⋅ u )I n = – p 0 n (6-30)
 3 

( – pI + μ ( ∇u + ( ∇u ) T ) )n = – p 0 n (6-31)

using the compressible/weakly compressible and the incompressible formulation,

respectively.

This is a normal stress condition together with a no-tangential-stress condition. When

μ > 0, Equation 6-30 or Equation 6-31 can be supplemented with a tangential velocity
condition

u⋅t = 0 (6-32)

If so, the no-tangential-stress condition is overridden. An issue with Equation 6-30 or

Equation 6-31 is that it does not strongly enforce unidirectional flow on the boundary.
If the prescribed pressure on an outlet is too high, parts of the outlet can actually have
inflow. This is not as much of an issue for the Navier–Stokes equations as it is an issue
for scalar transport equations solved along with the Navier–Stokes equations. Hence,
when applying the Pressure boundary condition at an outlet or inlet you can further
constrain the flow. With the Suppress backflow option

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 371
 --- μ ( ∇ ⋅ u )I n = – pˆ 0 n
 – pI + μ ( ∇u + ( ∇u ) T ) – 2
 3 
, (6-33)
( – pI + μ ( ∇u + ( ∇u ) T ) )n = – pˆ 0 n
pˆ ≤ p
0 0

the normal stress is adjusted to keep

u⋅n≥0 (6-34)

Equation 6-33 effectively means that the prescribed pressure is p0 if u⋅n ≥ 0, but
smaller at locations where u⋅n < 0. This means that Equation 6-33 does not completely
prevent backflow, but the backflow is substantially reduced. Backflow is suppressed
also when external forces are acting on the fluid, provided the magnitude of these
forces are of the same order as the dynamic pressure at the outlet.

A pressure condition can also be applied at an inlet. In this case, either the normal stress
is prescribed

n  – pI + μ ( ∇u + ( ∇u ) T ) – --- μ ( ∇ ⋅ u )I n = – pˆ 0
T 2
 3 
(6-35)
n ( – pI + μ ( ∇u + ( ∇u ) T ) )n = – pˆ 0
T

pˆ ≥ p
0 0

together with the tangential condition in Equation 6-32, or, a general flow direction
is prescribed.

--- μ ( ∇ ⋅ u )I n = – pˆ 0 ( r ⋅ n )
T  – pI + μ ( ∇u + ( ∇u ) T ) – 2
ru
 3  u
ˆ (r ⋅ n)
T ( – pI + μ ( ∇u + ( ∇u ) T ) )n = – p
ru 0 u
(6-36)
ˆp ≥ p
0 0
du
u – ( u ⋅ r u )r u = 0, r u = -----------
du

The “>” option is used with suppress backflow to have u ⋅ n ≤ 0 or u ⋅ r u ≥ 0 .

For incompressible single-phase flow, it is also allowed to specify the total pressure,
ptot, instead of the static pressure, pstat, on inlet and outlet boundaries. It is more

372 | CHAPTER 6: FLUID FLOW INTERFACES

useful, for example, in pump applications. The pressure is then prescribed at the
boundaries using Bernoulli’s principle,

1 2
p = p stat = p tot – --- ρ u (6-37)
2

The equation is imposed with two options: Average and Pointwise.

In the first option, pstat is prescribed by:

T T (6-38)
n ( – pI + μ ( ∇u + ( ∇u ) T ) )n = n ( – p stat I + μ ( ∇u + ( ∇u ) T ) )n

where ptot and |u|2 are averaged over the boundaries using the aveop operator:

1 2
p stat = aveop ( p tot ) – --- ρ ⋅ aveop ( u )
2

For the second option, Equation 6-37 is prescribed pointwise.

See Inlet, Outlet, Open Boundary, and for the individual node settings. Note that
some modules have additional theory sections describing options available with that
module.

Mass Sources for Fluid Flow

There are two types of mass sources in a Single-Phase Flow interface: point sources and
line sources.

These features require at least one of the following licenses: Battery

Design Module, CFD Module, Chemical Reaction Engineering Module,
Corrosion Module, Electrochemistry Module, Electrodeposition
Module, Fuel Cell & Electrolyzer Module, Microfluidics Module, Pipe
Flow Module, Polymer Flow Module, or Subsurface Flow Module.

POINT SOURCE
·
A point source is theoretically formed by taking a mass injection/ejection, Q (SI unit:
kg/(m3·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 (SI unit:
kg/s), this can be expressed as

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 373
 · ·
lim
δV → 0  Q = qp (6-39)
δV

An alternative way to form a point source/sink 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 volume, such as drag
and fluid displacement, need to be neglected.

The weak contribution

q· p test ( p )
·
is added to a point in the geometry. As can be seen from Equation 6-39, Q must tend
to plus or minus infinity as δV tends to zero. This means that in theory the pressure
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 6-39 corresponds to a finite pressure in

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 the source. A finer
mesh gives a smaller affected region, but also a more extreme pressure value. It is
important not to mesh too finely around a point source since the resulting pressure can
result in unphysical values for the density, for example. 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 (SI unit:
kg/(m3·s)), located within a tube with cross-sectional area 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 (SI unit: kg/(m·s)), this can be expressed as

· ·
lim
δS → 0  Q = ql (6-40)
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,

374 | CHAPTER 6: FLUID FLOW INTERFACES

but requires that effects on the fluid resulting from the physical object volume are
neglected.

The weak contribution

q· l test ( p )

is added to lines in 3D or to points in 2D (which represent cut-through views of lines).

Line sources can also be added to the axisymmetry line in 2D axisymmetry
components. It cannot, however, be added to geometrical lines in 2D because they
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.

For the Reacting Flow in Porous Media, Diluted Species interface, which
is available with the CFD Module, Chemical Reaction Engineering
Module, or Battery Design Module, these shared physics nodes are
renamed as follows:

• The Line Mass Source node is available as two nodes, one for the fluid
flow (Fluid Line Source) and one for the species (Species Line Source).
• The Point Mass Source node is available as two nodes, one for the fluid
flow (Fluid Point Source) and one for the species (Species Point Source).

Numerical Stability — Stabilization Techniques for Fluid Flow

The momentum equation (Equation 6-22 or Equation 6-24) is a (nonlinear)
convection-diffusion equation. Such equations can easily become unstable if
discretized using the Galerkin finite element method. Stabilized finite element
methods are usually necessary in order to obtain physical solutions. The stabilization
settings are found in the main Fluid Flow interface features. To display this section,
click the Show More Options button ( ) and select Stabilization in the Show More
Options dialog box.

There are three types of stabilization methods available for Navier–Stokes —

streamline diffusion, crosswind diffusion, and isotropic diffusion. Streamline

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 375
 diffusion and crosswind diffusion are consistent stabilization methods, whereas
isotropic diffusion is an inconsistent stabilization method.

For optimal functionality, the exact weak formulations of and constants in the
streamline diffusion and crosswind diffusion methods depend on the order of the
shape functions (basis functions) for the elements. The values of constants in the
streamline diffusion and crosswind diffusion methods follow Ref. 5 and Ref. 6.

STREAMLINE DIFFUSION
For strongly coupled systems of equations, the streamline diffusion method must be
applied to the system as a whole rather than to each equation separately. These ideas
were first explored by Hughes and Mallet (Ref. 8) and were later extended to Galerkin
least-squares (GLS) applied to the Navier–Stokes equations (Ref. 9). This is the
streamline diffusion formulation that COMSOL Multiphysics supports. The time-scale
tensor is the diagonal tensor presented in Ref. 10.

The time-scale tensors for time-dependent problems should in theory depend on a

time-scale that many references just set to the time-step taken by the time-solver, Δt
(see for example Ref. 9 and Ref. 10). This simple approach does not, however,
necessarily reflect on the actual time-scales in the physics. A typical example is reacting
flows where the time step is often guided by fast reactions, while the flow develops
relatively slowly. The COMSOL Multiphysics software can therefore replace Δt2 in the
time-scale tensor with measures of type ( 1 ⁄ ( Δt̃ ) 2 ) –1 , which are calculated from
projections of weak expressions in a fashion similar to those in Ref. 11. These measures
of the time scale are used when Use dynamic subgrid time scale check box is selected.
Streamline diffusion is active by default because it is necessary when convection is
dominating the flow.

The governing equations for incompressible flow are subject to the Babuška–Brezzi
condition, which states that the shape functions (basis functions) for pressure must be
of lower order than the shape functions for velocity. If the incompressible Navier–
Stokes equations are stabilized by streamline diffusion, it is possible to use equal-order
interpolation. Hence, streamline diffusion is necessary when using first-order elements
for both velocity and pressure. This applies also if the model is solved using geometric
multigrid (either as a solver or as a preconditioner) and at least one multigrid hierarchy
level uses linear Lagrange elements.

CROSSWIND DIFFUSION
Crosswind diffusion can also be formulated for systems of equations, and when applied
to the Navier–Stokes equations it becomes a shock-capturing operator. COMSOL

376 | CHAPTER 6: FLUID FLOW INTERFACES

Multiphysics supports the formulation in Ref. 9 with a shock-capturing viscosity of the
Hughes–Mallet type Ref. 8.

Incompressible flows do not contain shock waves, but crosswind diffusion is still useful
for introducing extra diffusion in sharp boundary layers and shear layers that otherwise
would require a very fine mesh to resolve.

Crosswind diffusion is active by default as it makes it easier to obtain a solution even if

the problem is fully resolved by the mesh. Crosswind diffusion also enables the iterative
solvers to use inexpensive presmoothers. If crosswind diffusion is deactivated, more
expensive preconditioners must be used instead.

ISOTROPIC DIFFUSION
Isotropic diffusion adds diffusion to the Navier–Stokes equations. Isotropic diffusion
significantly reduces the accuracy of the solution but does a very good job at reducing
oscillations. The stability of the continuity equation is not improved.

Numerical Stabilization and Iterative.

Solvers for Laminar Flow

The Navier–Stokes equations constitute a nonlinear equation system. A nonlinear
solver must hence be applied to solve the problem. The nonlinear solver iterates to
reach the final solution. In each iteration, a linearized version of the nonlinear system
is solved using a linear solver. In the time-dependent case, a time marching method
must also be applied. The default suggestions for each of these solver elements are
discussed below.

NONLINEAR SOLVER
The nonlinear solver method depends on if the model solves a stationary or a
time-dependent problem.

Stationary Solver
In the stationary case, a fully coupled, damped Newton method is applied. The initial
damping factor is low since a full Newton step can be harmful unless the initial values
are close to the final solution. The nonlinear solver algorithm automatically regulates
the damping factor in order to reach a converged solution.

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 377
 For advanced models, the automatically damped Newton method might not be robust
enough. A pseudo time-stepping algorithm can then be invoked. See Pseudo Time
Stepping for Laminar Flow Models.

Time-Dependent Solver
In the time-dependent case, the initial guess for each time step is (loosely speaking) the
previous time step, which is a very good initial value for the nonlinear solver. The
automatic damping algorithm is then not necessary. The damping factor in the
Newton method is instead set to a constant value slightly smaller than one. Also, for
the same reason, it suffices to update the Jacobian once per time step.

It is seldom worth the extra computational cost to update the Jacobian more than once
per time step. For most models it is more efficient to restrict the maximum time step
or possibly lower the damping factor in the Newton method.

LINEAR SOLVER
The linearized Navier–Stokes equation system has saddle point character, unless the
density depends on the pressure. This means that the Jacobian matrix has zeros on the
diagonal. Even when the density depends on the pressure, the equation system
effectively shares many numerical properties with a saddle point system.

For small 2D and 3D models, the default solver suggestion is a direct solver. Direct
solvers can handle most nonsingular systems and are very robust and also very fast for
small models. Unfortunately, they become slow for large models and their memory
requirement scales as somewhere between N1.5and N2, where N is the number of
degrees of freedom in the model. The default suggestion for large 2D and 3D models
is therefore the iterative GMRES solver. The memory requirement for an iterative
solver optimally scales as N.

GMRES is accelerated by a multigrid method, per default the smoothed aggregation

algebraic multigrid (SAAMG) method. The cost of SAAMG is typically very low
compared to the number of GMRES iterations necessary if no multigrid method is
used. As the name implies, SAAMG builds its coarser meshes algebraically, so the
application requires no additional meshes in order to employ SAAMG. In contrast, the
geometric multigrid (GMG) method requires actual meshes. If a sufficient number of
multigrid levels can be constructed, GMG is often faster than SAAMG. GMG is also
superior for cluster computations and for shared-memory computations with many
cores. When the default linear solver is GMRES, an optional, but deactivated, linear
solver node is available where GMRES is accelerated by GMG.

378 | CHAPTER 6: FLUID FLOW INTERFACES

Multigrid methods need smoothers, but the saddle point character of the linear system
restricts the number of applicable smoothers. The choices are further restricted by the
anisotropic meshes frequently encountered in fluid-flow problems. The efficiency of
the smoothers is highly dependent on the numerical stabilization. Iterative solvers
perform at their best when both Streamline Diffusion and Crosswind Diffusion are
active.

The default smoother for P1+P1 elements is SCGS. This is an efficient and robust
smoother specially designed to solve saddle point systems on meshes that contain
anisotropic elements. The SCGS smoother works well even without crosswind
diffusion. SCGS can sometimes work for higher-order elements, especially if Method in
the SCGS settings is set to Mesh element lines. But there is no guarantee for this, so the
default smoother for higher order elements is an SOR Line smoother. SOR Line
handles mesh anisotropy but does not formally address the saddle point character. It
does, however, function in practice provided that streamline diffusion and crosswind
diffusion are both active.

A different kind of saddle point character can arise if the equation system contains
ODE variables. Some advanced boundary conditions can add equations with such
variables. These variables must be treated with the Vanka algorithm. SCGS includes an
option to invoke Vanka. Models with higher-order elements must apply SCGS or use
the Vanka smoother. The latter is the default suggestion for higher-order elements, but
it does not work optimally for anisotropic meshes.

TIME-DEPENDENT SOLVERS
The default time-dependent solver for Navier–Stokes is the BDF method with
maximum order set to two. Higher BDF orders are not stable for transport problems
in general nor for Navier–Stokes in particular.

BDF methods have been used for a long time and are known for their stability.
However, they can have severe damping effects, especially the lower-order methods.
Hence, if robustness is not an issue, a model can benefit from using the generalized-α
method instead. Generalized-α is a solver which has properties similar to those of the
second-order BDF solver but it is much less diffusive.

Both BDF and generalized-α are per default set to automatically adjust the time step.
While this works well for many models, extra efficiency and accuracy can often be

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 379
 gained by specifying a maximum time step. It is also often beneficial to specify an initial
time step to make the solver progress smoothly in the beginning of the time series.

• Time-Dependent Solver
• Multigrid, Direct, Iterative, SCGS, SOR Line, and Vanka
• Stationary Solver

Pseudo Time Stepping for Laminar Flow Models

A stationary formulation has per definition no time derivatives and Equation 6-24
reduces to:

T
ρ ( u ⋅ ∇ )u = ∇ ⋅ [ – pI + μ ( ∇u + ( ∇u ) ) ] + F (6-41)

Solving Equation 6-41 requires a starting guess that is close enough to the final
solution. If no such guess is at hand, the fully transient problem can be solved instead.
This is, however, a rather costly approach in terms of computational time. An
intermediate approach is to add a fictitious time derivative to Equation 6-41:

u – nojac ( u ) T
ρ ------------------------------- + ρ ( u ⋅ ∇ )u = ∇ ⋅ [ – pI + μ ( ∇u + ( ∇u ) ) ] + F
Δt̃

where Δt̃ is a pseudo time step. Since u−nojac(u) is always zero, this term does not
affect the final solution. It does, however, affect the discrete equation system and
effectively transforms a nonlinear iteration into a step of size Δt̃ of a time-dependent
solver.

Pseudo time stepping is not active per default. The pseudo time step Δt̃ can be chosen
individually for each element based on the local CFL number:

h
Δt̃ = CFL loc ------
u

where h is the mesh cell size. A small CFL number means a small time step. It is
practical to start with a small CFL number and gradually increase it as the solution
approaches steady state.

If the automatic expression for CFLloc is set to the built-in variable CFLCMP, then the
automatic setting suggests a PID regulator for the pseudo time step in the default
solver. The PID regulator starts with a small CFL number and increases CFLloc as the
solution comes closer to convergence.

380 | CHAPTER 6: FLUID FLOW INTERFACES

The default manual expression is

1.3 min ( niterCMP, 9 ) +

if ( niterCMP > 20, 9 ⋅ 1.3 min ( niterCMP – 20, 9 ), 0 ) + (6-42)
if ( niterCMP > 40, 90 ⋅ 1.3 min ( niterCMP – 40, 9 ), 0)

The variable niterCMP is the nonlinear iteration number. It is equal to one for the first
nonlinear iteration. CFLloc starts at 1.3 and increases by 30% each iteration until it
reaches 1.3 9 ≈ 10.6 . It remains there until iteration number 20 at which it starts to
increase until it reaches approximately 106. A final increase after iteration number 40
then takes it to 1060. Equation 6-42 can, for some advanced flows, increase CFLloc
too slowly or too quickly. CFLloc can then be tuned for the specific application.

For details about the CFL regulator, see Pseudo Time Stepping.

Discontinuous Galerkin Formulation

Some boundary conditions are implemented using a discontinuous Galerkin
formulation. These boundary conditions include

• Wall — Slip, sliding walls, and moving walls (that is, walls with nonzero
translational velocity).
• Periodic Flow Condition
• Flow Continuity

The formulation used in the Fluid Flow interfaces in COMSOL Multiphysics is the
Symmetric Interior Penalty Galerkin method (SIPG). The SIPG method can be
regarded to satisfy the boundary conditions in an integral sense rather than pointwise.
More information on SIPG can be found in Ref. 15.

In particular, the SIPG formulation includes a penalty parameter that must be large
enough for the formulation to be coercive. The higher the value, the better the
boundary condition is fulfilled, but a too high value results in an ill-conditioned
equation system. The penalty parameter in COMSOL Multiphysics is implemented
according to Ref. 16.

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 381
 Particle Tracing in Fluid Flow
The Particle Tracing Module is available to assist with these types of modeling
problems.

It is possible to model particle tracing with COMSOL Multiphysics provided that the
impact of the particles on the flow field is negligible. First compute the flow field, and
then, as an analysis step, calculate the motion of the particles. The motion of a particle
is defined by Newton’s second law

2
d x
= F  t, x, 
dx
m
d t2  dt

where x is the position of the particle, m the particle mass, and F is the sum of all forces
acting on the particle. Examples of forces acting on a particle in a fluid are the drag
force, the buoyancy force, and the gravity force. The drag force represents the force
that a fluid exerts on a particle due to a difference in velocity between the fluid and the
particle. It includes the viscous drag, the added mass, and the Basset history term.
Several empirical expressions have been suggested for the drag force. One of those is
the one proposed by Khan and Richardson (Ref. 13). That expression is valid for
spherical particles for a wide range of particle Reynolds numbers. The particle
Reynolds number is defined as

u – u p 2rρ
Re p = ----------------------------
μ

where u is the velocity of the fluid, up the particle velocity, r the particle radius, ρ the
fluid density, and μ the dynamic viscosity of the fluid. The empirical expression for the
drag force according to Khan and Richardson is

2 -0.31 3.45
F = πr ρ u – u p ( u – u p ) [ 1.84Re p + 0.293Re p0.06 ]

The model Flow Past a Cylinder (Application Library path

COMSOL_Multiphysics/Fluid_Dynamics/cylinder_flow) demonstrates how to
add and set up particle tracing in a plot group using the Particle Tracing
with Mass node. It uses the predefined Khan-Richardson model for the
drag force and neglects gravity and buoyancy forces.

382 | CHAPTER 6: FLUID FLOW INTERFACES

References for the Single-Phase Flow, Laminar Flow Interfaces
1. G.G. Stokes, Trans. Camb. Phil. Soc., 8, pp. 287–305, 1845

2. P.M. Gresho and R.L. Sani, Incompressible Flow and the Finite Element Method,
Volume 2: Isothermal Laminar Flow, John Wiley & Sons, 2000.

3. G.K. Batchelor, An Introduction To Fluid Dynamics, Cambridge University Press,

1967.

4. R.L. Panton, Incompressible Flow, 2nd ed., John Wiley & Sons, 1996.

5. I. Harari and T.J.R. Hughes, “What are C and h? Inequalities for the Analysis and
Design of Finite Element Methods”, Comp. Meth. Appl. Mech. Engrg, vol. 97,
pp. 157–192, 1992.

6. Y. Bazilevs, V.M. Calo, T.E. Tezduyar, and T.J.R. Hughes, “YZβ Discontinuity
Capturing for Advection-dominated Processes with Application to Arterial Drug
Delivery”, [Link]. Meth. Fluids, vol. 54, pp. 593–608, 2007.

7. R.B. Bird,W.E. Stewart, and E.N. Lightfoot, Transport Phenomena, 2nd ed., John
Wiley&Sons, 2007.

8. T.J.R. Hughes and M. Mallet, “A New Finite Element Formulation for

Computational Fluid Dynamics: III. The Generalized Streamline Operator for
Multidimensional Advective-Diffusive System”, Comp. Meth. Appl. Mech. Engrg,
vol. 58, pp. 305–328, 1986.

9. G. Hauke and T.J.R. Hughes, “A Unified Approach to Compressible and

Incompressible Flows”, Comp. Meth. Appl. Mech. Engrg, vol. 113, pp. 389–395,
1994.

10. G. Hauke, “Simple Stabilizing Matrices for the Computation of Compressible

Flows in Primitive Variables”, Comp. Meth. Appl. Mech. Engrg, vol. 190, pp. 6881–
6893, 2001.

11. M.-C. Hsu, Y. Bazilevs, V.M. Cali, T.E. Tezduyar, and T.J.R. Hughes, “Improving
stability of stabilized and multiscale formulations in flow simulations at small time
steps”, Comp. Meth. Appl. Mech. Engrg, vol. 199, pp. 828–840, 2010.

12. D.J. Tritton, Physical Fluid Dynamics, 2nd ed., Oxford University Press, 1988.

13. J.M. Coulson and J.F. Richardson, “Particle Technology and Separation
Processes”, Chemical Engineering, Volume 2, Butterworth-Heinemann, 2002.

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 383
 14. J.L. Guermond, P. Minev, and J. Shen, “An overview of projection methods for
incompressible flows”, Comp. Meth. Appl. Mech. Engrg, vol. 195, pp. 6011–6045,
2006.

15. B. Rivière, Discontinuous Galerkin Methods for Solving Elliptic and Parabolic
Equations, SIAM, 2008.

16. Y. Epshteyn and B. Rivière, “Estimation of penalty parameters for symmetric

interior penalty Galerkin methods”, J. Computational and Applied Mathematics,
vol. 206, pp. 843–872, 2007.

17. R.P. Chhabra and J.F. Richardson, Non-Newtonian Flow and Applied Rheology,
2nd ed., Elsevier, 2008.

18. Y. Bazilevs and T.J.R. Hughes, “Weak imposition of Dirichlet boundary conditions
in fluid mechanics”, Computers and Fluids, vol. 36, pp. 12–26, 2007.

384 | CHAPTER 6: FLUID FLOW INTERFACES

T he o r y f o r t he D arc y’ s Law In t erfac e
The Darcy’s Law Interface theory is described in this section:

• About Darcy’s Law

• Darcy’s Law — Equation Formulation
• Storage Model
• Average Linear Velocity
• References for the Darcy’s Law Interface

About Darcy’s Law

In a porous medium, the global transport of momentum by shear stresses in the fluid
is often negligible, because the pore walls impede momentum transport to the fluid
outside the individual pores. A detailed description, down to the resolution of every
pore, is not practical in most applications. 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 (or gas) provide
a complete mathematical model suitable for a wide variety of applications involving
porous media flows, for which the pressure gradient is the major driving force.

Darcy’s law describes fluid movement through interstices in a porous medium.

Because the fluid loses considerable energy to frictional resistance within pores, flow
velocities in porous media are very low. The Darcy’s Law interface can be applied to
small-scale tasks in chemical engineering as well as to large-scale geophysical or
hydrological tasks such as water moving in an aquifer or stream bank, oil migrating to
a well, and even magma rising through the earth to a chamber in a volcano (see Ref. 1,
Ref. 2, Ref. 3, and Ref. 4). Also set up multiple Darcy’s Law interfaces to model
multiphase flows involving more than one mobile phase.

Darcy’s law describes flow in porous media driven by gradients in the hydraulic
potential field, which has units of pressure. For many applications it is convenient to
represent the total hydraulic potential or the pressure and the gravitational
components with equivalent heights of fluid or head. Division of potential by the fluid
weight can simplify modeling because units of length make it straightforward to
compare to many physical data. Consider, for example, fluid levels in wells, stream
heights, topography, and velocities. The physics interface also supports specifying

THEORY FOR THE DARCY’S LAW INTERFACE | 385

 boundary conditions and result evaluation using hydraulic head and pressure head. In
the physics interface, pressure is always the dependent variable.

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 (6-43)
μ

In this equation, u is the Darcy’s velocity or specific discharge vector (SI unit: m/s);
κ is the permeability of the porous medium (SI unit: m2); μ is the fluid’s dynamic
viscosity (SI unit: Pa·s); p is the pore pressure (SI unit: Pa) and ρ is the density of the
fluid (SI unit: kg/m3).

• The above equation formulation is called linear Darcy law. The

applicability of this formulation is discussed in the chapter About
Darcian and Non-Darcian Flow in the Porous Media Flow Module
User’s Guide.
• Permeability can be defined in different ways, either directly or based
on predefined permeability models. These are described in detail in the
chapter Permeability Models.
• For a detailed overview of the permeability models available in each
product visit [Link]

The Darcy’s Law interface combines Darcy’s law with the continuity equation

∂ ρε
( p ) + ∇ ⋅ ( ρu ) = Q m (6-44)
∂t

In the above equation, ρ is the fluid density (SI unit: kg/m3), εp is the porosity, and
Qm is a mass source term (SI unit: kg/(m3·s)). 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.

For large-scale applications it might be necessary to take gravity effects into account.
Darcy’s law then applies when the gradient in hydraulic potential drives fluid
movement in the porous medium. Darcy’s law then has the form:

386 | CHAPTER 6: FLUID FLOW INTERFACES

 κ
u = – --- ( ∇p + ρg ) (6-45)
μ

• See the section Gravity Effects in the Subsurface Flow Module User’s
Guide.
• Note that gravity effects are only included in some modules. For a
detailed overview of the functionality available in each product visit
[Link]
• Gravity effects are not active by default. Select the check box Include
gravity to activate the acceleration of gravity. Setting the elevation D to
zero also turns off gravity effects.

Storage Model
Inserting Darcy’s law (Equation 6-43) into the continuity equation produces the
generalized governing equation

∂ ρε κ
( p ) + ∇ ⋅ ρ – --- ( ∇p ) = Q m (6-46)
∂t μ

Represent this equation fully in COMSOL Multiphysics because relationships between

density or permeability can be freely specified, for example, and pressure, temperature,
concentration, and so on.

Expand the time-derivative term in Equation 6-46

∂ ρε = ∂-----
ρ ∂ε p
( p) ε p - + ρ --------
∂t ∂t ∂t

Define the porosity and the density as functions of the pressure, and apply the chain
rule

∂ρ ∂ε p ∂ρ ∂p ∂ε p ∂p
ε p ------ + ρ -------- = ε p ------ ------ + ρ -------- ------
∂t ∂t ∂p ∂t ∂p ∂t

Insert the definition of fluid compressibility χf = (1/ρ)(∂ρ/∂p) to the right-hand side and
rearrange to arrive at

∂( ρε p ) ∂ε p ∂p ∂p
---------------- = ρ  ε p χ f + -------- ------ = ρS ------
∂t  ∂p  ∂t ∂t

THEORY FOR THE DARCY’S LAW INTERFACE | 387

 Using this relation, the generalized governing equation (Equation 6-46) takes the
following form:

∂p κ
ρS ------ + ∇ ⋅ ρ – --- ( ∇p ) = Q m (6-47)
∂t μ

In this equation, S is the storage coefficient (SI unit: 1/Pa), which can be interpreted
as the weighted compressibility of the porous material and the fluid. The storage S can
be an expression involving results from a solid-deformation equation or an expression
involving temperatures and concentrations from other analyses. The Darcy’s Law
interface implements Equation 6-47 in the Porous Medium node, which explicitly
includes different storage models to choose from, such as linearized storage which
defines S (SI unit: 1/Pa) using the compressibility of fluids χf and of the porous matrix
χp:

S = ε p χ f + ( 1 – ε p )χ p ,

or the poroelastic storage where

S = εp χf .

The Storage Model node is only available for the Subsurface Flow
Module and the Porous Media Flow Module. For a detailed overview of
the functionality available in each product visit https://
[Link]/products/specifications/.

Average Linear Velocity

Because fluids typically occupy only 10% to 50% of a porous medium, it follows that
velocities within the pore channels exceed the Darcy velocity, u, on the order of two
to ten times. For clarity, the physics interface includes the average linear velocity within
the pores, uα, (also termed the seepage velocity) defined as uα = u/εp, where εp is the
porosity.

References for the Darcy’s Law Interface

1. J. Bear, Hydraulics of Groundwater, McGraw-Hill, 1979.

388 | CHAPTER 6: FLUID FLOW INTERFACES

2. S.E. Ingebritsen and W.E. Sanford, Groundwater in Geologic Processes, Cambridge
University Press, 1998.

3. N.H. Sleep and K. Fujita, Principles of Geophysics, Blackwell Science, 1997.

4. D.L. Turcotte and G. Schubert, Geodynamics, Cambridge University Press, 2002.

5. J. Bear, Dynamics of Fluids in Porous Media, Elsevier Scientific Publishing, 1972.

6. Ö. Akgiray and A.M. Saatçı, “A New Look at Filter Backwash Hydraulics,” Water
Science and Technology: Water Supply, vol. 1, no. 2, pp. 65–72, 2001.

7. L. Klinkenberg, “The permeability of porous media to liquids and gases,” Drilling

and Production Practice, Am. Petroleum Inst., pp. 200–213, 1941.

8. Yu-Shu Wu and others, “Gas Flow in Porous Media with Klinkenberg Effects,”
Transport in Porous Media, vol. 32, pp. 117–137, 1998.

THEORY FOR THE DARCY’S LAW INTERFACE | 389

 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.

390 | CHAPTER 6: 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 | 391

 ∂ ε
( ρ ) + ∇ ⋅ ( ρu ) = Q m (6-48)
∂t p

ρ-  ∂u
+ ( u ⋅ ∇ ) ----- =
---- u
εp  ∂ t εp
(6-49)
1 T 2   –1 Q m
–∇ 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 of the porous medium, and
• Qm (SI unit: kg/(m3·s)) is a mass source or 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 flow) check box is selected, the term (u · ∇)(u/
εp) on the left-hand side of Equation 6-49 is disabled.

The mass source, Qm, accounts for mass deposit and mass creation within the domains.
The mass exchange is assumed to occur at zero velocity.

The Forchheimer and Ergun drag options add a viscous force proportional to the
square of the fluid velocity, F = −ρβ|u|u, on the right-hand side of Equation 6-49; see
References for the Darcy’s Law Interface for details.

In case of a flow with variable density, Equation 6-48 and Equation 6-49 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

392 | CHAPTER 6: FLUID FLOW INTERFACES

and the continuity equation (Equation 6-48) reduces to

ρ∇ ⋅ u = Q m

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. Fluid Mech.,
vol. 550, pp. 149–173, 2006.

THEORY FOR THE BRINKMAN EQUATIONS INTERFACE | 393

 Theory for the Coupling of Fluid
Flow to Electrochemical Reactions
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 (6-50)
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 (6-51)
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 (6-52)
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.

394 | CHAPTER 6: FLUID FLOW INTERFACES

 7

Heat Transfer

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 Electrodeposition Module has 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 Electrodeposition Module irrespective of whether a separate
Heat Transfer Module license is purchased.

In this chapter:

• Coupling of Heat Transfer to Electrochemical Reactions

395
 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 Electrochemical Heating multiphysics node that becomes available in
the model builder tree under the Multiphysics node if there is both a Heat Transfer
interface and an Electrochemistry interface available in the same component. It 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. It also sets 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 [Link]
(domain, Joule heating and porous electrode reactions) and [Link] (boundary,
electrode surface reactions), where xxx is the electrochemistry interface identifier.

• Electrochemistry Interfaces
• Multiphysics Coupling Nodes

396 | CHAPTER 7: HEAT TRANSFER

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 ) (7-1)

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 (7-2)
 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 7-2 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

∂E eq, m ΔS m
------------------
- = -----------
-
∂T nm F

the local heat source due to the electrochemical conversion process becomes

COUPLING OF HEAT TRANSFER TO ELECTROCHEMICAL REACTIONS | 397

 ∂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
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.

398 | CHAPTER 7: HEAT TRANSFER

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 | 399

400 | CHAPTER 7: HEAT TRANSFER
 8

Level Set and Phase Field

This chapter describes the Level Set and Phase Field interfaces, found under the
Mathematics>Moving Interface branch ( ).

In this chapter:

• The Level Set Interface

• The Phase Field Interface
• Theory for the Level Set Interface
• Theory for the Phase Field Interface

401
 T he L e v e l S e t In t erfac e
The Level Set (ls) interface ( ), found under the Mathematics>Moving Interface
branch ( ) when adding an interface, is used to track moving interfaces in fluid-flow
models by solving a transport equation for the level set function. Simulations using the
Level Set interface are always time dependent since the position of an interface almost
always depends on its history.

The main node is the Level Set Model feature, which adds the level set equation and
provides an interface for defining the level set properties and the velocity field.

When this physics interface is added, the following default nodes are also added in the
Model Builder — Level Set Model, No Flow (the default boundary condition), Initial
Values, and Initial Values, Fluid 2. Then, from the Physics toolbar, add other nodes that
implement, for example, boundary conditions. You can also right-click Level Set 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 ls.

STABILIZATION
To display this sections, click the Show More Options button ( ) and select
Stabilization in the Show More Options dialog box.

There are two stabilization methods available — Streamline diffusion and Crosswind
diffusion. Both are active by default and should remain selected for optimal
performance.

ADVANCED SETTINGS
To display this sections, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box.

402 | CHAPTER 8: LEVEL SET AND PHASE FIELD

Specify the Convective term as Nonconservative form (default) or Conservative form.

DISCRETIZATION
By default, the Level Set interface uses Linear elements.

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

• Conservative and Nonconservative Form

• Domain, Boundary, and Pair Nodes for the Level Set Interface
• Theory for the Level Set Interface

Domain, Boundary, and Pair Nodes for the Level Set Interface
The Level Set Interface has the following domain, boundary and pair nodes described.

• Continuity • Periodic Condition (see Periodic

• Initial Values Boundary Conditions in the
COMSOL Multiphysics Reference
• Inlet
Manual)
• Level Set Model
• Symmetry1
• No Flow
• Thin Barrier
• Open Boundary
• Outlet1
1 Described for the Laminar Flow interface.

Boundary conditions for axial symmetry boundaries are not required. For
the symmetry axis at r = 0, the software automatically provides a suitable
boundary condition and adds an Axial Symmetry node that is valid on the
axial symmetry boundaries only.

THE LEVEL SET INTERFACE | 403

 In the COMSOL Multiphysics Reference Manual see Table 2-4 for links
to common sections and Table 2-5 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.

Level Set Model

The Level Set Model node adds the following transport equation governing a level set
function φ

∂φ ∇φ
+ u ⋅ ∇φ = γ∇ ⋅  ε∇φ – φ ( 1 – φ ) ----------
∂t  ∇φ 

and provides the options to define the associated level set parameters and the velocity
field.

LEVEL SET PARAMETERS

Enter a value or expression for the Reinitialization parameter γ (SI unit: m/s). The
default is 1 m/s.

Enter a value or expression for the Parameter controlling interface thickness els
(SI unit: m). The default expression is [Link]/2, which means that the value is half
of the maximum mesh element size in the region through which the interface passes.

CONVECTION
Enter values or expressions for the components (u, v, and w in 3D, for example) of the
Velocity field u (SI unit: m/s). The applied velocity field transports the level set
function through convection.

Initial Values
Use the Initial Values node to define the initial values of the level set variable.

INITIAL VALUES
The initial positions of the two fluids, and consequently the separating interface, can
be specified in two ways. The level set function can be specified explicitly, using any
type of variable or expression. Alternatively the fluid occupying the current domain
selection can be specified. Using the former method, a Time Dependent study step can

404 | CHAPTER 8: LEVEL SET AND PHASE FIELD

directly be solved. Using the latter method, a Phase Initialization study step is needed
in order to initialize the level set function across the fluid-fluid interface.

Specify the Level set variable as one of the following:

• To specify the fluid occupying the domain, select Specify phase (default). Then select
the check box Fluid 1 ( φ = 0 ) or Fluid 2 ( φ = 1 ).
• For User defined enter a value or expression for the level set variable φ .

If the Phase Initialization ( ) study step is being used, for the

initialization to work it is crucial that there are two Initial Values nodes.
One of the Initial Values nodes should use Specify phase: Fluid 1 ( φ = 0 )
and the other Specify phase: Fluid 2 ( φ = 1 ). The initial fluid-fluid
interface is then automatically placed on all interior boundaries between
both phases. The smooth initialization is not used in domains with User
defined initial values.

See Initializing the Level Set Function.

Inlet

LEVEL SET CONDITION

Specify Level Set Condition according to one of the following options:

• Fluid 1 ( φ = 0 )
• Fluid 2 ( φ = 1 )
• Specify level set function explicitly

When the Specify level set function explicitly is selected, the level set function φ must
be specified explicitly. The value must be in the range from 0 to 1, where the default
is 0.

No Flow
The No Flow node adds a boundary condition that represents boundaries where there
is no flow across the boundary. This is the default boundary condition.

THE LEVEL SET INTERFACE | 405

 Open Boundary
Use this node to set up 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 value of the level set function 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 Level Set interface.

LEVEL SET CONDITION

Specify Level Set Condition according to one of the following options:

• Fluid 1 ( φ = 0 )
• Fluid 2 ( φ = 1 )
• Specify level set function explicitly

When the Specify level set function explicitly is selected, the level set function φ must
be specified explicitly. The value must be in the range from 0 to 1, where the default
is 0.

Thin Barrier
The Thin Barrier feature is available on interior boundaries and introduces a
discontinuity in the level set variable across the boundary. A No Flow condition is
prescribed on each side. This node can be used to avoid meshing thin structures.

Continuity
The Continuity condition is suitable for pairs where the boundaries match; it prescribes
that the level set variable is continuous across the pair.

The parts of the boundary where a source boundary lacks a corresponding destination
boundary and vice versa will get conditions from other boundary conditions under the
physics interface acting as fallback boundary conditions on the nonoverlapping parts.

406 | CHAPTER 8: LEVEL SET AND PHASE FIELD

By default, the No Flow node is used as fallback unless another feature has been
selected for the boundary.

About Identity and Contact Pairs

LOCATION IN USER INTERFACE

Right-click the physics interface and select Pairs>Continuity.

Ribbon
Physics tab with the physics interface selected:

Pairs>Continuity

THE LEVEL SET INTERFACE | 407

 The Phase Field Interface
The Phase Field (pf) interface ( ), found under the Mathematics>Moving Interface
branch ( ) when adding a physics interface, is used to track moving interfaces by
solving two transport equations, one for the phase field variable, φ , and one for the
mixing energy density, ψ. The position of the interface is determined by minimizing
the free energy.

The main node is the Phase Field Model feature, which adds the phase field equations
and provides an interface for defining the phase field model properties.

When this physics interface is added, the following default nodes are also added in the
Model Builder — Phase Field Model, Wetted Wall (the default boundary condition), Initial
Values, and Initial Values, Fluid 2. Then, from the Physics toolbar, add other nodes that
implement, for example, boundary conditions. You can also right-click Phase Field 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 pf.

ADVANCED SETTINGS
To display this sections, click the Show More Options button ( ) and select Advanced
settings options in the Show More Options dialog box.

Specify the Convective term as Nonconservative form (default) or Conservative form.

DISCRETIZATION
By default, the Phase Field interface uses Linear elements.

408 | CHAPTER 8: LEVEL SET AND PHASE FIELD

DEPENDENT VARIABLES
This interface defines the dependent variables (fields) Phase field variable φ and Phase
field help variable ψ. If required, edit the name, but dependent variables must be
unique within a model.

• Conservative and Nonconservative Form

• Domain, Boundary, and Pair Nodes for the Phase Field Interface
• Theory for the Phase Field Interface

Domain, Boundary, and Pair Nodes for the Phase Field Interface
includes 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 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.

• Periodic Condition (see Periodic Boundary

• Continuity
Conditions in the COMSOL Multiphysics
• Initial Values
Reference Manual)
• Inlet
• Phase Field Model
• Interior Wetted Wall
• Symmetry1
1
• Outlet
• Wetted Wall
1
Described for the Laminar Flow interface.

In the COMSOL Multiphysics Reference Manual see Table 2-4 for links
to common sections and Table 2-5 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 PHASE FIELD INTERFACE | 409

 Phase Field Model
The Phase Field Model node adds the equations described in . The node defines the
associated phase field parameters including surface tension and interface thickness.

PHASE FIELD PARAMETERS

Define the following phase field parameters. Enter a value or expression for the:

• Surface tension coefficient σ (SI unit: N/m).

• Parameter controlling interface thickness epf (SI unit: m). The default expression is
[Link]/2, which means that the value is half of the maximum mesh element size
in the region through which the interface passes.
• Mobility tuning parameter χ (SI unit: m·s/kg). This parameter determines the time
scale of the Cahn-Hilliard diffusion and it thereby also governs the diffusion-related
time scale for the interface. Select User defined (default) or Calculate from velocity.
For User defined enter a value or expression for the mobility tunning parameter χ.
The default is 1 m·s/kg, which is a good starting point for most models.

For Calculate from velocity enter a value for the expected velocity at the interface U
(SI unit: m/s). χ is then computed as:
Uh max
χ = ------------------
3 2σε

where hmax is the largest mesh cell size.

Keep the χ parameter value large enough to maintain a constant interface

thickness but still low enough to not damp the convective motion. A too
high mobility can also lead to excessive diffusion of droplets.

EXTERNAL FREE ENERGY

Add a source of external free energy to the phase field equations. This modifies the last
term on the right-hand side of the equation:

2
ε ∂f
ψ = – ∇ ⋅ ε ∇φ + ( φ – 1 )φ +  -----
2 2
 λ  ∂φ

The external free energy f (SI unit: J/m3) is a user-defined free energy. In most cases,
the external free energy can be set to zero. Manually differentiate the expression for

410 | CHAPTER 8: LEVEL SET AND PHASE FIELD

the external free energy with respect to φ and then enter it into the φ -derivative of
external free energy field ∂f ⁄ ∂φ .

CONVECTION
Enter values or expressions for the components (u, v, and w in 3D, for example) of the
Velocity field u (SI unit: m/s). The applied velocity field transports the phase field
variables through convection.

Initial Values
Use the Initial Values node to define the initial values of the phase field variable.

INITIAL VALUES
The initial positions of the two fluids, and consequently the fluid-fluid interface, can
be specified in two ways. The phase field variable can be specified explicitly, using any
type of variable or expression. Alternatively the fluid occupying the current domain
selection can be specified. Using the former method, a Time Dependent study step can
directly be solved. Using the latter method, a Phase Initialization study step is needed
in order to initialize the phase field function across the fluid-fluid interface.

Specify the Phase field variable as one of the following:

• To specify the fluid occupying the domain, select Specify phase (default). Then select
the check box Fluid 1 ( φ = – 1 ) or Fluid 2 ( φ = 1 ).
• For User defined enter a value or expression for the phase field variable φ .

If the Phase Initialization ( ) study step is being used, for the

initialization to work it is crucial that there are two Initial Values nodes.
One of the Initial Values nodes is set to Specify phase: Fluid 1 ( φ = – 1 )
and the other to Specify phase: Fluid 2 ( φ = 1 ). The initial fluid-fluid
interface is then automatically placed on all interior boundaries between
both phases. The smooth initialization is not used in domains with User
defined initial values.

THE PHASE FIELD INTERFACE | 411

 Inlet

SETTINGS
Specify Phase field Condition according to one of the following options:

• Fluid 1 ( φ = – 1 )
• Fluid 2 ( φ = 1 )
• Specify phase field function explicitly

When Specify phase field function explicitly is selected, the phase field function φ must
be specified in the entire domain. The value must be in the range from -1 to 1, where
the default is 1.

Wetted Wall
The Wetted Wall node is the default boundary condition representing wetted walls.
Along a wetted wall the contact angle for the fluid, θw, is specified, and across it, the
mass flow is zero. This is prescribed by

2 2
n ⋅ ε ∇φ = ε cos ( θ w ) ∇φ

in combination with

γλ
n ⋅ -----2- ∇ψ = 0
ε

The contact angle θw can be defined directly or from Young's equation, which
considers the components of the forces in the plane of the surface:

σ cos ( θ w ) + γ s2 = γ s1 (8-1)

where γs1 is the surface energy density on the fluid 1 — solid (wall) interface and γs2
is the surface energy density on the fluid 2 — solid (wall) interface.

WETTED WALL
Select an option from the Specify contact angle list — Directly (the default) or Through
Young’s equation. For Directly enter a value or expression for the Contact angle θw (SI
unit: rad). The default value is π/2 radians. For Through Young’s equation enter values
or expressions for Phase 1-Solid surface energy density γs1 (SI unit: J/m2) and Phase
2-Solid surface energy density γs2 (SI unit: J/m2).

412 | CHAPTER 8: LEVEL SET AND PHASE FIELD

Interior Wetted Wall
The Interior Wetted Wall feature is available on interior boundaries. It is similar to the
Wetted Wall condition except that it applies on both sides of an interior boundary and
introduces a discontinuity of the phase field variables across the boundary. This node
can be used to avoid meshing thin structures.

Along an interior wetted wall the contact angle for the fluid, θw, is specified on both
sides of the boundary, and across it, the mass flow is zero.

WETTED WALL
Enter a value or expression for the Contact angle θw. The default value is π/2 rad.

Continuity
The Continuity condition is suitable for pairs where the boundaries match; it prescribes
that the phase field variables are continuous across the pair.

The parts of the boundary where a source boundary lacks a corresponding destination
boundary and vice versa will get conditions from other boundary conditions under the
physics interface acting as fallback boundary conditions on the nonoverlapping parts.
By default, the Wetted Wall node is used as fallback unless another feature has been
selected for the boundary.

About Identity and Contact Pairs

LOCATION IN USER INTERFACE

Right-click the physics interface and select Pairs>Continuity.

Ribbon
Physics tab with the physics interface selected:

Pairs>Continuity

THE PHASE FIELD INTERFACE | 413

 Theory for the Level Set Interface
Fluid flow with moving interfaces or boundaries occur in a number of different
applications, such as fluid-structure interaction, multiphase flows, and flexible
membranes moving in a liquid. One way to track moving interfaces is to use a level set
method. A certain contour line of the globally defined function, the level set function,
then represents the interface between the phases. For the fluid-fluid interface can be
advected with an arbitrary velocity field.

In this section:

• The Level Set Method

• Conservative and Nonconservative Form
• Initializing the Level Set Function
• Variables For Geometric Properties of the Interface
• Reference for the Level Set Interface

The Level Set Method

The level set method is a technique to represent moving interfaces or boundaries using
a fixed mesh. It is useful for problems where the computational domain can be divided
into two domains separated by an interface. Each of the two domains can consist of
several parts. Figure 8-1 shows an example where one of the domains consists of two
separated parts. The interface is represented by a certain level set or isocontour of a
globally defined function, the level set function φ . In COMSOL Multiphysics, φ is a
smooth step function that equals zero (0) in one domain and one (1) in the other.
Across the interface, there is a smooth transition from zero to one. The interface is

414 | CHAPTER 8: LEVEL SET AND PHASE FIELD

defined by the 0.5 isocontour, or level set, of φ . Figure 8-2 shows the level set
representation of the interface in Figure 8-1.

Figure 8-1: An example of two domains divided by an interface. In this case, one of the
domains consists of two parts. Figure 8-2 shows the corresponding level set representation.

Figure 8-2: A surface plot of the level set function corresponding to Figure 8-1.

The physics interface solves Equation 8-2 in order to move the interface with the
velocity field u:

∂φ ∇φ
+ u ⋅ ∇φ = γ∇ ⋅  ε∇φ – φ ( 1 – φ ) ---------- (8-2)
∂t ∇φ

The terms on the left-hand side give the correct motion of the interface, while those
on the right-hand side are necessary for numerical stability. The parameter, ε,
determines the thickness of the region where φ varies smoothly from zero to one and
is typically of the same order as the size of the elements of the mesh. By default, ε is

THEORY FOR THE LEVEL SET INTERFACE | 415

 constant within each domain and equals the largest value of the mesh size, h, within
the domain. The parameter γ determines the amount of reinitialization or stabilization
of the level set function. It needs to be tuned for each specific problem. If γ is too small,
the thickness of the interface might not remain constant and oscillations in φ can
appear because of numerical instabilities. On the other hand, if γ is too large the
interface moves incorrectly. A suitable value for γ is the maximum magnitude of the
velocity field u.

Conservative and Nonconservative Form

If the velocity is divergence free, that is, if

∇⋅u = 0 (8-3)

the volume (area for 2D problems) bounded by the interface should be conserved if
there is no inflow or outflow through the boundaries. To obtain exact numerical
conservation in cases where Equation 8-3 is not fully satisfied, switch to the
conservative form

∂φ ∇φ
+ ∇ ⋅ ( uφ ) = γ∇ ⋅  ε∇φ – φ ( 1 – φ ) ---------- (8-4)
∂t  ∇φ 

in Settings window for .

Using the conservative level set form, exact numerical conservation of the integral of
φ is obtained. However, the nonconservative form is better suited for numerical
calculations and usually converges more easily. The nonconservative form, which is the
default form, only conserves the integral of the level set function approximately, but
this is sufficient for most applications.

Initializing the Level Set Function

If the study type Transient with Phase Initialization is used in the model, the level set
variable is first initialized so that it varies smoothly between zero and one over the
interface. For that study, two study steps are created, Phase Initialization and Time
Dependent. The Phase Initialization step solves for the distance to the initial interface,
Dwi. The Time Dependent step then uses the initial condition for the level set function
according to the following expression:

1
φ 0 = -------------------------
–D ⁄ ε
-
1 + e wi

416 | CHAPTER 8: LEVEL SET AND PHASE FIELD

in domains initially outside the interface and

1
φ 0 = -----------------------
D ⁄ε
-
1 + e wi

in domains initially inside the interface. Here, inside refers to domains where φ < 0.5
and outside refers to domains where φ > 0.5 .

f the Transient with Phase Initialization ( ) study is being used, for the
initialization to work it is crucial that there are two Initial Values nodes.
One of the Initial Values nodes should use Specify phase: Fluid 1 ( φ = 0 )
and the other Specify phase: Fluid 2 ( φ = 1 ). The initial fluid-fluid
interface is then automatically placed on all interior boundaries between
both phases. The smooth initialization is not used in domains with User
defined initial values.

• The Level Set Interface

• Studies and Solvers and Time Dependent with Initialization in the
COMSOL Multiphysics Reference Manual

Variables For Geometric Properties of the Interface

Geometric properties of the interface are often needed. The unit normal to the
interface is given by

∇φ
n = ---------- (8-5)
∇φ φ = 0.5

This variable is available in the physics interface as the interface normal [Link].

Reference for the Level Set Interface

1. E. Olsson and G. Kreiss, “A Conservative Level Set Method for Two Phase Flow,”
J. Comput. Phys., vol. 210, pp. 225–246, 2005.

THEORY FOR THE LEVEL SET INTERFACE | 417

 Theory for the Phase Field Interface
The following Phase Field theory is described in this section:

• About the Phase Field Method

• The Equations for the Phase Field Method
• Conservative and Nonconservative Forms
• Additional Sources of Free Energy
• Initializing the Phase Field Function
• Variables and Expressions
• Reference for the Phase Field Interface

About the Phase Field Method

The phase field method offers an attractive alternative to more established methods for
solving multiphase flow problems. Instead of directly tracking the interface between
two fluids, the interfacial layer is governed by a phase field variable, φ . The surface
tension force is added to the Navier-Stokes equations as a body force by multiplying
the chemical potential of the system by the gradient of the phase field variable.

The evolution of the phase field variable is governed by the Cahn-Hilliard equation,
which is a 4th-order PDE. The Phase Field interface decomposes the Cahn-Hilliard
equation into two second-order PDEs.

For the level set method, the fluid interface is simply advected with the flow field. The
Cahn-Hilliard equation, on the other hand, does not only convect the fluid interface,
but it also ensures that the total energy of the system diminishes correctly. The phase
field method thus includes more physics than the level set method.

The free energy of a system of two immiscible fluids consists of mixing, bulk distortion,
and anchoring energy. For simple two-phase flows, only the mixing energy is retained,
which results in a rather simple expression for the free energy.

The Equations for the Phase Field Method

The free energy is a functional of a dimensionless phase field parameter, φ :

418 | CHAPTER 8: LEVEL SET AND PHASE FIELD

   --2- ε ∇φ + f ( φ, T ) dV =
1
 ftot dV
2 2
F ( φ, ∇φ, T ) =


where ε is a measure of the interface thickness. Equation 8-6 describes the evolution
of the phase field parameter:

∂φ ∂f tot ∂f tot
+ ( u ⋅ ∇ )φ = ∇ ⋅ γ∇  –∇⋅ (8-6)
∂t ∂φ ∂ ∇φ 

where ftot (SI unit: J/m3) is the total free energy density of the system, and u
(SI unit: m/s) is the velocity field for the advection. The right-hand side of
Equation 8-6 aims to minimize the total free energy with a relaxation time controlled
by the mobility γ (SI unit: m3·s/kg).

The free energy density of an isothermal mixture of two immiscible fluids is the sum
of the mixing energy and elastic energy. The mixing energy assumes the
Ginzburg-Landau form:

1 2 λ 2 2
f mix ( φ, ∇φ ) = --- λ ∇φ + --------2- ( φ – 1 )
2 4ε

where φ is the dimensionless phase field variable, defined such that the volume fraction
of the components of the fluid are (1+ φ )/2 and (1− φ )/2. The quantity λ
(SI unit: N) is the mixing energy density and ε (SI unit: m) is a capillary width that
scales with the thickness of the interface. These two parameters are related to the
surface tension coefficient, σ (SI unit: N/m), through the equation

2 2λ
σ = ----------- --- (8-7)
3 ε

The PDE governing the phase field variable is the Cahn-Hilliard equation:

∂φ
+ u ⋅ ∇φ = ∇ ⋅ γ ∇G (8-8)
∂t

where G (SI unit: Pa) is the chemical potential and γ (SI unit: m3·s/kg) is the mobility.
The mobility determines the time scale of the Cahn-Hilliard diffusion and must be
large enough to retain a constant interfacial thickness but small enough so that the
convective terms are not overly damped. In COMSOL Multiphysics the mobility is
determined by a mobility tuning parameter that is a function of the interface thickness
γ = χε2. The chemical potential is:

THEORY FOR THE PHASE FIELD INTERFACE | 419

 2
2 φ(φ – 1)
G = λ – ∇ φ + ----------------------
2
- (8-9)
ε

The Cahn-Hilliard equation forces φ to take a value of 1 or −1 except in a very thin

region on the fluid-fluid interface. The Phase Field interface breaks Equation 8-8 up
into two second-order PDEs:

∂φ γλ
+ u ⋅ ∇φ = ∇ ⋅ -----2- ∇ψ (8-10)
∂t ε

2 2
ψ = – ∇ ⋅ ε ∇φ + ( φ – 1 )φ (8-11)

Conservative and Nonconservative Forms

If the velocity field is divergence free, that is, if

∇⋅u = 0 (8-12)

the volume (area for 2D problems) bounded by the interface should be conserved if
there is no inflow or outflow through the boundaries. To obtain exact numerical
conservation in cases where Equation 8-12 is not fully satisfied, switch to the
conservative form

∂φ γλ
+ ∇ ⋅ uφ = ∇ ⋅ -----2- ∇ψ
∂t ε

Using the conservative phase field form, exact numerical conservation of the integral
of φ is obtained. However, the nonconservative form is better suited for numerical
calculations and usually converges more easily. The nonconservative form, which is the
default form, only conserves the integral of the phase field function approximately, but
this is sufficient for most applications.

When the Phase Field interface is coupled to a fluid flow interface by means of ,
conservation of the integral of φ using the nonconservative form can be improved
provided that the discretization order of the phase field variables is equal to or lower
than the order of the pressure.

420 | CHAPTER 8: LEVEL SET AND PHASE FIELD

Additional Sources of Free Energy
In some cases, the expression for the free energy can include other sources. It is
possible to incorporate these by modifying Equation 8-11:

2
ε ∂f
ψ = – ∇ ⋅ ε ∇φ + ( φ – 1 )φ +  -----
2 2
(8-13)
 λ  ∂φ

where f is a user-defined free energy (SI unit: J/m3).

The expression for the external free energy must be manually

differentiated with respect to φ and then entered into the ∂f ⁄ ∂φ field.
In most cases, the external free energy is zero.

Initializing the Phase Field Function

If the study type Transient with Phase Initialization is used in the model, the phase field
variable is first initialized so that it varies smoothly between zero and one over the
interface. For this study, two study steps are created, Phase Initialization and Time
Dependent. The Phase Initialization step solves for the distance to the initial interface,
Dwi. The Time Dependent step then uses the initial condition for the phase field
function according to the following expression:

D wi
φ 0 = – tanh  ----------
2ε

in Fluid 1 and

D wi
φ 0 = tanh  ----------
 2ε

THEORY FOR THE PHASE FIELD INTERFACE | 421

 in Fluid 2. These expressions are based on a steady, analytic solution to Equation 8-10
and Equation 8-11 for a straight, non-moving interface.

If the Transient with Phase Initialization ( ) study is being used, for the
initialization to work it is crucial that there are two Initial Values nodes.
One of the Initial Values nodes is set to Specify phase: Fluid 1 ( φ = – 1 )
and the other to Specify phase: Fluid 2 ( φ = 1 ). The initial fluid-fluid
interface is then automatically placed on all interior boundaries between
both phases. The smooth initialization is not used in domains with User
defined initial values.

Studies and Solvers in the COMSOL Multiphysics Reference Manual

Variables and Expressions

The physics interface defines the chemical potential, which can be rewritten in terms
of the dependent variable ψ,

λψ
G = ------2-
ε

and the surface tension force F = G∇ φ .

Geometric properties of the interface are often needed. The unit normal to the
interface is given by

∇φ
n = ---------- (8-14)
∇φ φ = 0.5

This variable is available in the physics interface as the interface normal [Link].

The mean curvature (SI unit: 1/m) of the interface can be computed by entering the
following expression:

G
κ = 2 ( 1 + φ ) ( 1 – φ ) ----
σ

422 | CHAPTER 8: LEVEL SET AND PHASE FIELD

Reference for the Phase Field Interface
1. P. Yue, C. Zhou, J.J. Feng, C.F. Ollivier-Gooch, and H.H. Hu, “Phase-field
Simulations of Interfacial Dynamics in Viscoelastic Fluids Using Finite Elements with
Adaptive Meshing,” J. Comp. Phys., vol. 219, pp. 47–67, 2006.

THEORY FOR THE PHASE FIELD INTERFACE | 423

424 | CHAPTER 8: LEVEL SET AND PHASE FIELD
 9

Multiphysics Coupling Nodes

The Electrodeposition 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.

425
 In this chapter, the following multiphysics couplings nodes are described:

• Deforming Electrode Surface • Space Charge Density Coupling

• Nondeforming Boundary • Boundary Electrolyte Potential
• Electrochemical Heating Coupling

• Potential Coupling

Deforming Electrode Surface

Use the Deforming Electrode Surface multiphysics coupling to model deformation of the
geometry due to an electrochemical deposition-dissolution process.

The node uses the deposition-dissolution velocity of an Electrode Surface boundary in

an Electrochemistry interface to apply a deformation velocity on to a deforming
boundary.

Special conditions for the tangential velocity at points (2D) and edges (3D) shared
with nondeforming surfaces apply, as described in the theory section.

The node, available as a multiphysics coupling node, is only applicable when both the
Electrochemistry interface (Primary/Secondary/Tertiary Current Distribution or
Lithium-Ion Battery or Battery with Binary Electrolyte) and a Deformed Geometry
node are added to a component.

MOVING BOUNDARY SMOOTHING

Certain electrode deformation problems are inherently unstable. The Moving
Boundary Smoothing will stabilize the moving boundary by applying a fictitious
surface tension. Use the Moving boundary smoothing tuning parameter, δmbs, to control
smoothing. A higher value means more smoothing.

RECOMMENDED SETTINGS IN THE COUPLED DEFORMED GEOMETRY

INTERFACE
Predefined multiphysics interfaces are available from the model wizard that will
automatically add and set up the coupling between a current distribution interface and
the deformed geometry node. However, you can also add a Deformed Geometry
interface manually to an already existing model.

The following settings are recommended in the Deformed Geometry interface if you
are manually setting up the coupling between a Deformed Geometry interface and an

426 | CHAPTER 9: MULTIPHYSICS COUPLING NODES

Electrochemistry interface using the Deforming Electrode Surface and Nondeforming
Boundary multiphysics coupling nodes:

• At the Deformed Geometry interface node, change the Geometry shape order to 1
and Mesh smoothing type to Hyperelastic
• Clear all the check boxes at the default Prescribed Mesh Displacement boundary
feature node
• Add Free Deformation domain node and make sure it is selected on the deforming
domains of the geometry

Tangential Velocities at the Intersection Between a Depositing and a

Nondepositing Boundary

Nondeforming Boundary
Use the Nondeforming Boundary multiphysics coupling to define boundaries that do not
undergo deformation in the normal direction.

A Nondeforming Boundary can be applied to external boundaries of an electrolyte and

is typically used to specify an insulator, a nondissolving/depositing electrode surface
or a symmetry boundary in a problem.

The node, available as a multiphysics coupling node, is only applicable when both the
Electrochemistry interface (Primary/Secondary/Tertiary Current Distribution or
Lithium-Ion Battery or Battery with Binary Electrolyte) and a Deformed Geometry
node are added to a component.

Zero normal displacement is implemented using pointwise constraints, which may be

more numerically stable, but should typically only be used for planar boundaries since
the boundary is effectively fixed in the tangential direction if the curvature of the
boundary is nonzero.

As a rule of thumb: use Zero normal displacement for planar boundaries and Zero normal
velocity for curved boundaries.

For 3D components, and when Zero normal displacement is selected, the deformation
may be further stabilized by enabling the Allow deformation along specified line only.
The specified line must be parallel to the boundary in the nondeformed geometry.

See also the Deforming Electrode Surface node.

| 427
 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

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.

428 | CHAPTER 9: MULTIPHYSICS COUPLING NODES

Boundary Electrolyte Potential Coupling
The Boundary Elements Potential Coupling node couples the electrolyte phase
potential, computed in a finite-element-based (FEM) physics interface to the
electrolyte phase potential of a boundary-element-based (BEM) physics interface.

COUPLED INTERFACES
Specify the FEM interface in the Source list and the BEM interface in the Destination
list.

| 429
430 | CHAPTER 9: MULTIPHYSICS COUPLING NODES
 10

Glossary

This Glossary of Terms contains application-specific terms used in the

Electrodeposition 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.

431
 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 (friction forces) 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.

432 | CHAPTER 10: 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 | 433

 COMSOL Multiphysics using the Tertiary Current Distribution, Nernst-Planck
interface (and the Transport of Diluted Species interface). The Nernst-Planck equation
is often combined with an electroneutrality condition.

Nernst-Planck-Poisson equation In certain situations, for instance when striving to

resolve the electrochemical double layer at an electrode, and electroneutrality 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.

434 | CHAPTER 10: 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 | 435

436 | CHAPTER 10: GLOSSARY
I n d e x
A absolute pressure 292, 352 Brinkman equations interface 344
activation overpotential 121, 128, 151 theory 391
adsorption 197 Butler-Volmer and Tafel expressions
amperometric sensing 148 tertiary current distribution 71
analyte 148 Butler-Volmer equation 41
anodes 32 electrode kinetics 128
anodic Tafel equation 131 secondary current distribution 121
anodic transfer coefficient 122 Butler–Volmer equation
Application Libraries window 25 electroanalysis 153
application library examples
C Cahn-Hilliard equation 418
convection and diffusion 176
cathodes 32
Darcy’s law 312
cathodic charge transfer coefficient 122
electrode, shell 111
cathodic Tafel equation 131
infinite electrolyte 68
CFL number
laminar flow 290
settings 289, 347
migration in electric field 176
charge transfer reaction 121
secondary current distribution 63
charge transfer reactions 94
storage model 320
checklist, for modeling 51
transport of diluted species 170
chemical equilibrium 211
Arrhenius parameters 213
chemical potential variable 422
atmosphere/gauge (node) 330
chronoamperometry 148
average linear velocity 388
common settings 22
B boundary current source (node) 115 concentration (node)
boundary electrolyte potential 102, 237 transport of diluted species 180
boundary nodes continuity (node) 406, 413
Brinkman equations 347 convection 257
Darcy’s law interface 312 convective terms, diluted species 249
electrochemistry interfaces 85 coulometry 148
electrode, shell 111 creeping flow (spf) interface 284
free and porous media flow 336 current (node) 236
level set 403 current density (node) 236
phase field 409 current distribution on edges, BEM inter-
surface reactions 241 face 81
transport of diluted species 171, 233 current source (node) 114
boundary stress (node) 304 cyclic voltammetry 148
Brinkman equations 391

INDEX| 437
 D Darcy velocity 257, 326 electrochemistry 87
Darcy’s law interface 310 electrode, shell 112
theory 385 electrode current (node) 106
Debye length 36 electrode current density (node) 105
deforming electrode surface (node) 426 electrode current source (node) 87
depositing electrode (node) 113 electrode line current source (node) 68
documentation 23 electrode points current source (node)
domain nodes 70
Brinkman equations 347 electrode potential (node) 107
Darcy’s law 312 electrode power (node) 106
electrochemistry interfaces 85 electrode reaction (node)
electrophoretic transport interface electrochemistry 94
233 electrode surface (node) 90
free and porous media flow 336 electrode symmetry axis current source
level set 403 (node) 69
phase field 409 electrode, shell interface 110
transport of diluted species 171 theory 146
double layer capacitance (node) 100 electrode-electrolyte boundary interface

E edge electrode (node) 67 (node)

edge nodes current distribution 104

Darcy’s law interface 312 electrode-electrolyte interface coupling

electrochemistry interfaces 85 (node)

electrode, shell 111 free and porous media flow 323, 341

surface reactions 241 transport of diluted species 190

electric insulation (node) electrode-electrolyte interfaces 32

electrode, shell 115 electrodeposition, primary interface 160

electric potential (node) electrodeposition, secondary interface

electrode, shell 115 160

electric reference potential (node) 109 electrodeposition, tertiary

electroanalysis interface 117 Nernst-Planck interface 160

theory 148 electrodes 31

electroanalysis, definition 148 electrolysis 31

electrochemical cells 32 electrolyte 120

electrochemical impedance spectrosco- electrolyte (node)

py (EIS) 148 primary and secondary current distri-

electrochemical sensing 148 bution 63

electrode 120 tertiary current distribution 75

electrode (node) electrolyte current (node) 102

438 | I N D E X
 electrolyte current density (node) 103 transport of diluted species 182
electrolyte current source (node) 88 fracture flow (node) 333
electrolyte line current source (node) 69 free and porous media flow interface 334
electrolyte points current source (node) theory 390
70 Freundlich exponent 263
electrolyte potential 123 fully developed flow 299
electrolyte potential (node) 102
G galvanic cells 31
electrolyte symmetry axis current
gas reacting fluids 206, 217
source (node) 69
general stress (boundary stress condi-
electrolyte-electrode domain interface
tion) 304
(node) 100
Gibbs free energy 215
electrolytes 31
Ginzburg-Landau equation 419
electromagnetic heat source (multiphys-
gravity 309
ics coupling) 428
ground (node) 115
electroneutrality 36
H harmonic perturbation (node) 107
electrophoretic transport interface 227
heterogeneous rate constant 153
elevation 322
hydraulic head (node) 330
emailing COMSOL 25
Hygroscopic Swelling 200
equilibrium potential 121
Equilibrium Reaction I inflow (node) 179, 239
theory for 247 initial values (node)
equilibrium reaction (node) 186 Brinkman equations 351
equilibrium reaction group (node) 222 corroding electrode surface node 108
external short circuit (node) 107 Darcy’s law 320
depositing electrode surface node 108
F faradaic current 45
electrode, shell 113
Faraday’s constant 122
free and porous media flow 341
Faraday’s law 253
level set 404, 411
Faraday’s laws of electrolysis 152
primary and secondary current distri-
Fick diffusion laws 150
bution 64
flow continuity (node) 306
single-phase, laminar flow 293
flow rate in SCCMs 299
spf interfaces 293
fluid flow
surface reactions 243
Brinkman equations theory 391
tertiary current distribution 78
fluid properties (node) 337
transport of diluted species 176
flux (node) 238
initializing functions 416, 421
transport of diluted species 180, 238
inlet (node) 296
flux discontinuity (node) 182
single-phase flow 296
Darcy’s law 327

INDEX| 439
 insulation (node) 89, 237 electromagnetic heat source (node)
interface normal variable 417, 422 428
interior wetted wall (node) 413
N Nernst equation 153
internet resources 23
Nernst-Einstein relation 175, 192, 196,
intrinsic volume averages 391
253
irreversible reaction 211
Nernst-Planck equations 35, 118
K knowledge base, COMSOL 26 Nernst-Planck-Poisson equations 36
Nernst-Planck-Poisson Equations inter-
L laminar flow interface 285
face 225
Langmuir constant 263
no flow (node) 327
leaking wall, wall boundary condition
level set 405
295, 343
no flux (node) 178
level set functions, initializing 416, 421
no slip, wall boundary condition 294, 342
level set interface 402
no viscous stress (open boundary) 304
theory 414
nodes, common settings 22
level set model (node) 404
nonconservative formulations 249
line mass source (node)
nondeforming boundary (node) 427
fluid flow 308
non-faradaic reactions (node) 108
species transport 184
normal current density (node) 114
line source
normal stress, normal flow (boundary
species transport 251
stress condition) 305
liquid reacting fluids 206, 217
local O Ohm’s law 60, 120, 254
CFL number 289, 347 ohmic drop 149
open boundary (node)
M mass based concentrations (node) 176
level set 406
mass source (node)
single-phase flow 303
Brinkman equations 350
spf interfaces 303
Darcy’s law 319
transport of diluted species 185
mathematics, moving interfaces
outflow (node)
level set 402
electrophoretic transport 239
phase field 408
transport of diluted species 180
theory 414, 418
outlet (node) 300
modeling checklist 51
single-phase flow 300
monolayer adsorption 275
spf interfaces 300
moving interfaces 418
overpotential 40, 121
MPH-files 25
multiphase flow theory 414, 418 P pair nodes
multiphysics couplings Brinkman equations 347

440 | I N D E X
 Darcy’s law interface 312 porous electrodes 63, 121
electrochemistry interfaces 85 porous matrix double layer capacitance
electrode, shell 111 (node) 89
electrophoretic transport interface porous media and subsurface flow
233 Brinkman equations interface 344
free and porous media flow 336 Darcy’s law interface 310
level set 403 free and porous media flow interface
phase field 409 334
surface reactions 241 theory, Brinkman equations 391
transport of diluted species 171 theory, free and porous media flow
partially saturated porous media (node) 390
194 porous media transport properties
periodic condition (node) 66 (node) 190, 194
transport of diluted species 183 Porous Medium (node)
periodic flow condition (node) 305 Brinkman equations 338, 348
permeability models 317 potential (node) 237
pervious layer (node) 331 potentiometry 148
phase field interface 408 potentiostat 156
theory 418 pressure (node) 324, 326, 328
phase field model (node) 410 pressure head (node) 330
physics interfaces, common settings 22 pressure point constraint (node) 307
point mass source (node) primary current distribution 33
fluid flow 307 primary current distribution interface 60
species transport 185 theory 118
point nodes pseudo time stepping
Brinkman equations 347 settings 289, 347
Darcy’s law interface 312
R reacting fluids, gases and liquids 206, 217
electrochemistry interfaces 85
Reacting Volume 177
electrode, shell 111
reaction (node) 210
free and porous media flow 336
reaction coefficients (node) 189
surface reactions 241
reaction thermodynamics (node) 223
transport of diluted species 171
reactions (node)
point source
surface reactions 243
species transport 250
tertiary current distribution 78
porous electrode (node) 64, 76
transport of diluted species 177
porous electrode coupling (node) 189
reference electrode (node) 109
free and porous media flow 323, 340
resistive film 126
porous electrode reaction (node) 88
retardation factor 263

INDEX| 441
 reversible reaction 211 surface tension force variable 422
reversible reaction group (node) 220 symmetry (node) 303
Darcy’s law 327
S SCCM, flow rate in 299
electrochemistry 89
secondary current distribution 33
spf interfaces 303
secondary current distribution interface
transport of diluted species 182
60
theory 118 T Tafel equation 131
SEMI standard E12-0303 298 Tafel law 41
separator (node) technical support, COMSOL 25
current distribution 77 tertiary current distribution 33
single-phase flow interface tertiary current distribution interface
laminar flow 285 theory 118
sliding wall 296 tertiary current distribution,
slip, wall boundary condition 294, 342 Nernst-Planck interface 71
species (node) 215 theory
species activity (node) 223 Brinkman equations 391
species group (node) 223 Darcy’s law 385
species source (node) 237 electroanalysis interface 148
species thermodynamics (node) 224 electrode, shell interface 146
standard cubic centimeters per minute free and porous media flow 390
299 level set 414
standard flow rate 299 phase field 418
standard settings 22 primary current distribution interface
stoichiometric coefficients 215 118
Stokes equations 284 secondary current distribution inter-
Stokes flow 284 face 118
stratified porous media 261 surface reactions 274
superficial volume average, porous me- tertiary current distribution interface
dia 391 118
superficial volume averages, porous me- transport of diluted species in porous
dia 257 media interface 246
supporting electrolyte 148 transport of diluted species interface
Supporting Electrolytes 253 245
surface concentration (node) 244 thickness
surface equilibrium reaction (node) 188 fracture 203
surface properties (node) 242 out-of-plane 322
surface reactions interface 240 thin barrier (node)
theory 274 level set 406

442 | I N D E X
 thin diffusion barrier (node) 186
thin electrode surface (node) 101
Thin Impermeable Barrier 186
tortuosity factors 259
traction boundary conditions 304
transport of diluted species in porous
media interface 170
theory 246
transport of diluted species interface 166
theory 245

V variables
level set interface 417
phase field interface 422
voltammetry, cyclic 148
volume averages 391
volume force (node) 293, 351
free and porous media flow 340
spf interfaces 293

W wall (node)
free and porous media flow 342
single-phase flow 294
websites, COMSOL 26
wetted wall (node) 412

INDEX| 443
444 | I N D E X