Fuel Cell &

Electrolyzer Module
User’s Guide
Fuel Cell & Electrolyzer Module User’s Guide
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Part number: CM025101

C o n t e n t s

Chapter 1: Introduction

About the Fuel Cell & Electrolyzer Module 24

What Can the Fuel Cell & Electrolyzer Module Do? . . . . . . . . . 24
Fuel Cell & Electrolyzer Module Physics Interface Guide . . . . . . . . 25
Common Physics Interface and Feature Settings and Nodes . . . . . . 29
Where Do I Access the Documentation and Application Libraries? . . . . 29

Overview of the User’s Guide 32

Chapter 2: Modeling with Electrochemistry

Introduction to Electrochemistry Modeling 36

What Is Electrochemistry? . . . . . . . . . . . . . . . . . . . 36
Electrochemical Applications . . . . . . . . . . . . . . . . . . 37
Fundamentals of Electrochemistry Modeling . . . . . . . . . . . . 37
Current Distribution Cases and Choosing the Right Interface to
Model an Electrochemical Cell . . . . . . . . . . . . . . . . 39
Understanding the Different Approximations for Conservation of
Charge in Electrolytes . . . . . . . . . . . . . . . . . . . 40
Modeling Electrochemical Reactions . . . . . . . . . . . . . . . 44
Double Layer Capacitance . . . . . . . . . . . . . . . . . . . 51
Porous Electrodes . . . . . . . . . . . . . . . . . . . . . . 52
Boundary Conditions for Running and Controlling Electrochemical
Cells . . . . . . . . . . . . . . . . . . . . . . . . . . 53
Aspects to Consider When Modeling Batteries or Fuel Cells . . . . . . 54
Modeling Cyclic Voltammetry . . . . . . . . . . . . . . . . . . 56
Common Simplifications When Modeling Electrochemical Cells . . . . . 57
Before You Start Building Your Model . . . . . . . . . . . . . . . 59
Meshing Advice . . . . . . . . . . . . . . . . . . . . . . . 60
Solving Electrochemical Models . . . . . . . . . . . . . . . . . 61
Postprocessing Your Solution . . . . . . . . . . . . . . . . . . 65

CONTENTS |3
 Chapter 3: AC/DC Interfaces

The Electrostatics Interface 70

Domain, Boundary, Edge, Point, and Pair Nodes for the
Electrostatics Interface . . . . . . . . . . . . . . . . . . . 72
Charge Conservation . . . . . . . . . . . . . . . . . . . . . 74
Conduction Loss (Time-Harmonic) . . . . . . . . . . . . . . . . 75
Initial Values . . . . . . . . . . . . . . . . . . . . . . . . 76
Space Charge Density . . . . . . . . . . . . . . . . . . . . . 77
Zero Charge . . . . . . . . . . . . . . . . . . . . . . . . 77
Ground . . . . . . . . . . . . . . . . . . . . . . . . . . 77
Electric Potential . . . . . . . . . . . . . . . . . . . . . . . 78
Surface Charge Density . . . . . . . . . . . . . . . . . . . . 78
External Surface Charge Accumulation . . . . . . . . . . . . . . 79
Electric Displacement Field . . . . . . . . . . . . . . . . . . . 79
Periodic Condition . . . . . . . . . . . . . . . . . . . . . . 80
Thin Low Permittivity Gap . . . . . . . . . . . . . . . . . . . 81
Line Charge . . . . . . . . . . . . . . . . . . . . . . . . . 81
Line Charge (on Axis) . . . . . . . . . . . . . . . . . . . . . 82
Line Charge (Out-of-Plane) . . . . . . . . . . . . . . . . . . . 82
Point Charge . . . . . . . . . . . . . . . . . . . . . . . . 83
Point Charge (on Axis) . . . . . . . . . . . . . . . . . . . . 83
Change Cross Section . . . . . . . . . . . . . . . . . . . . . 84
Change Thickness (Out-of-Plane). . . . . . . . . . . . . . . . . 84
Charge Conservation, Piezoelectric . . . . . . . . . . . . . . . . 85

The Electric Currents Interface 86

Domain, Boundary, Edge, Point, and Pair Nodes for the Electric
Currents Interface . . . . . . . . . . . . . . . . . . . . . 88
Current Conservation . . . . . . . . . . . . . . . . . . . . . 90
Initial Values . . . . . . . . . . . . . . . . . . . . . . . . 92
External Current Density . . . . . . . . . . . . . . . . . . . 92
Current Source . . . . . . . . . . . . . . . . . . . . . . . 93
Electric Insulation . . . . . . . . . . . . . . . . . . . . . . 93
Boundary Current Source . . . . . . . . . . . . . . . . . . . 93
Normal Current Density . . . . . . . . . . . . . . . . . . . . 94
Distributed Impedance. . . . . . . . . . . . . . . . . . . . . 94

4 | CONTENTS
 Contact Impedance . . . . . . . . . . . . . . . . . . . . . . 95
Sector Symmetry . . . . . . . . . . . . . . . . . . . . . . . 96
Line Current Source . . . . . . . . . . . . . . . . . . . . . 97
Line Current Source (on Axis). . . . . . . . . . . . . . . . . . 98
Point Current Source . . . . . . . . . . . . . . . . . . . . . 98
Point Current Source (on Axis) . . . . . . . . . . . . . . . . . 99
Piezoresistive Material . . . . . . . . . . . . . . . . . . . . . 99

Theory for the Electrostatics Interface 101

Charge Relaxation Theory . . . . . . . . . . . . . . . . . . 101
Electrostatics Equations . . . . . . . . . . . . . . . . . . . 103
The Electrostatics Interface in Time Dependent or Frequency
Domain Studies . . . . . . . . . . . . . . . . . . . . . 104

Theory for the Electric Currents Interface 105

Electric Currents Equations in Steady State . . . . . . . . . . . . 105

Chapter 4: Electrochemistry Interfaces

The Primary and Secondary Current Distribution Interfaces 108

The Primary Current Distribution and Secondary Current Distribution
Interfaces . . . . . . . . . . . . . . . . . . . . . . . 108
Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . 111
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 111
Porous Electrode. . . . . . . . . . . . . . . . . . . . . . 112
Periodic Condition . . . . . . . . . . . . . . . . . . . . . 113
Thin Electrolyte Layer . . . . . . . . . . . . . . . . . . . . 113
Edge Electrode. . . . . . . . . . . . . . . . . . . . . . . 114
Electrode Line Current Source . . . . . . . . . . . . . . . . 115
Electrolyte Line Current Source . . . . . . . . . . . . . . . . 115
Electrode Symmetry Axis Current Source . . . . . . . . . . . . 116
Electrolyte Symmetry Axis Current Source . . . . . . . . . . . . 116
Electrode Point Current Source . . . . . . . . . . . . . . . . 116
Electrolyte Point Current Source. . . . . . . . . . . . . . . . 116
Electrode Current . . . . . . . . . . . . . . . . . . . . . 117

CONTENTS |5
 The Tertiary Current Distribution, Nernst-Planck Interface 118
The Tertiary Current Distribution, Nernst-Planck Interface . . . . . 118
Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . 122
Porous Electrode. . . . . . . . . . . . . . . . . . . . . . 123
Separator. . . . . . . . . . . . . . . . . . . . . . . . . 124
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 125
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 125
Ion Exchange Membrane . . . . . . . . . . . . . . . . . . . 126
Ion Exchange Membrane Boundary . . . . . . . . . . . . . . . 126
Thin Electrolyte Layer . . . . . . . . . . . . . . . . . . . . 127

Shared Physics Features in the Current Distribution Interfaces

128
Domain, Boundary, Pair, Edge, and Point Nodes for the
Electrochemistry Interfaces . . . . . . . . . . . . . . . . 128
Electrode. . . . . . . . . . . . . . . . . . . . . . . . . 130
Highly Conductive Porous Electrode . . . . . . . . . . . . . . 130
Electrode Current Source . . . . . . . . . . . . . . . . . . 130
Electrolyte Current Source . . . . . . . . . . . . . . . . . . 131
Porous Electrode Reaction . . . . . . . . . . . . . . . . . . 131
Porous Matrix Double Layer Capacitance . . . . . . . . . . . . 132
Insulation . . . . . . . . . . . . . . . . . . . . . . . . . 132
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 132
Electrode Surface. . . . . . . . . . . . . . . . . . . . . . 133
Electrode Reaction . . . . . . . . . . . . . . . . . . . . . 136
Double Layer Capacitance . . . . . . . . . . . . . . . . . . 142
Internal Electrode Surface . . . . . . . . . . . . . . . . . . 142
Electrolyte Potential . . . . . . . . . . . . . . . . . . . . 143
Electrolyte Current . . . . . . . . . . . . . . . . . . . . . 143
Electrolyte Current Density. . . . . . . . . . . . . . . . . . 144
Thin Electrode Layer . . . . . . . . . . . . . . . . . . . . 144
Electrode-Electrolyte Boundary Interface. . . . . . . . . . . . . 144
Electric Ground . . . . . . . . . . . . . . . . . . . . . . 145
Electric Potential . . . . . . . . . . . . . . . . . . . . . . 146
Electrode Current Density . . . . . . . . . . . . . . . . . . 146
Electrode Current . . . . . . . . . . . . . . . . . . . . . 146
Electrode Power . . . . . . . . . . . . . . . . . . . . . . 147
Harmonic Perturbation . . . . . . . . . . . . . . . . . . . 147

6 | CONTENTS
Electrode Potential . . . . . . . . . . . . . . . . . . . . . 148
External Short . . . . . . . . . . . . . . . . . . . . . . . 148
Initial Values for Dissolving-Depositing Species . . . . . . . . . . 148
Non-Faradaic Reactions . . . . . . . . . . . . . . . . . . . 149
Reference Electrode . . . . . . . . . . . . . . . . . . . . 149
Electric Reference Potential . . . . . . . . . . . . . . . . . . 149
Circuit Terminal . . . . . . . . . . . . . . . . . . . . . . 150

The Electrode, Shell Interface 151

Boundary, Edge, Point, and Pair Nodes for the Electrode, Shell
Interface. . . . . . . . . . . . . . . . . . . . . . . . 152
Electrode . . . . . . . . . . . . . . . . . . . . . . . . . 153
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 154
External Current Density . . . . . . . . . . . . . . . . . . 154
Current Source . . . . . . . . . . . . . . . . . . . . . . 154
Normal Current Density . . . . . . . . . . . . . . . . . . . 155
Electric Insulation . . . . . . . . . . . . . . . . . . . . . 155
Boundary Current Source . . . . . . . . . . . . . . . . . . 155
Ground . . . . . . . . . . . . . . . . . . . . . . . . . 155
Electric Potential . . . . . . . . . . . . . . . . . . . . . . 156

The Electroanalysis Model Wizard Entry 157

Theory for the Current Distribution Interfaces 158

The Nernst-Planck Equations . . . . . . . . . . . . . . . . . 158
Domain Equations for Primary and Secondary Current Distributions . . 159
Electrochemical Reactions and the Difference Between a Primary and
a Secondary Current Distribution . . . . . . . . . . . . . . 160
Domain Equations for Tertiary Current Distributions Using the
Nernst-Planck Equations and Electroneutrality . . . . . . . . . 163
Mass Fluxes and Sources Due to Electrochemical Reactions . . . . . 164
Deposition-Dissolution Rates, Growth Velocities, and Thicknesses on
an Electrode Surface . . . . . . . . . . . . . . . . . . . 165
Stoichiometric Coefficients for Double Layer Capacitive Charging . . . 166
Film Resistance . . . . . . . . . . . . . . . . . . . . . . 166
Equilibrium Potentials and the Nernst Equation . . . . . . . . . . 167
Electrode Kinetics Expressions . . . . . . . . . . . . . . . . 168
Theory for Specific Current Distribution Feature Nodes . . . . . . . 173

CONTENTS |7
 References . . . . . . . . . . . . . . . . . . . . . . . . 180

Theory for Electrochemical Heat Sources 181

Joule Heating Due to Charge Transport . . . . . . . . . . . . . 182
Heating Due to Electrochemical Reactions . . . . . . . . . . . . 182
Heating Due to Heat of Mixing . . . . . . . . . . . . . . . . 183

Theory for the Electrode, Shell Interface 185

Governing Equations . . . . . . . . . . . . . . . . . . . . 185
Coupling to Other Physics Interfaces . . . . . . . . . . . . . . 185

Theory for Electroanalysis 187

Electroanalytical Methods . . . . . . . . . . . . . . . . . . 187
Supporting Electrolyte . . . . . . . . . . . . . . . . . . . . 187
Domain Equations for the Electroanalysis Case . . . . . . . . . . 188
Electrode Boundary Conditions in the Electroanalysis Model . . . . . 190
The Electroanalytical Butler-Volmer Equation . . . . . . . . . . . 192
Counter Electrodes and Overall Charge Balance . . . . . . . . . . 193

Electrode Potentials and Reference Electrodes 194

Reference Electrodes . . . . . . . . . . . . . . . . . . . . 194
Boundary Conditions Using Reference Electrode Potentials. . . . . . 195
Nodes for Handling Electrode Potentials and Reference Electrodes. . . 195

Chapter 5: Fuel Cell and Electrolyzer Interfaces

The Hydrogen Fuel Cell and Water Electrolyzer Interfaces 198

Electrolyte Phase . . . . . . . . . . . . . . . . . . . . . . 202
Electronic Conducting Phase . . . . . . . . . . . . . . . . . 202
Gas Phase . . . . . . . . . . . . . . . . . . . . . . . . 203
Membrane . . . . . . . . . . . . . . . . . . . . . . . . 204
Current Collector . . . . . . . . . . . . . . . . . . . . . 204
Gas Diffusion Layer . . . . . . . . . . . . . . . . . . . . . 204
Gas Diffusion Electrode . . . . . . . . . . . . . . . . . . . 205
Flow Channel . . . . . . . . . . . . . . . . . . . . . . . 206
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 206

8 | CONTENTS
 Initial Values, O2 Domains . . . . . . . . . . . . . . . . . . 206
Initial Values, H2 Domains . . . . . . . . . . . . . . . . . . 206
Reaction Sources . . . . . . . . . . . . . . . . . . . . . . 207
Gas Diffusion Electrode Reaction. . . . . . . . . . . . . . . . 207
Porous Double Layer Capacitance . . . . . . . . . . . . . . . 208
Overview of the Boundary Nodes in the Hydrogen Fuel Cell and
Water Electrolyzer Interfaces. . . . . . . . . . . . . . . . 208
Insulation . . . . . . . . . . . . . . . . . . . . . . . . . 209
Electrolyte Potential . . . . . . . . . . . . . . . . . . . . 209
Electrolyte Current Density. . . . . . . . . . . . . . . . . . 210
Electric Ground . . . . . . . . . . . . . . . . . . . . . . 210
Electric Potential . . . . . . . . . . . . . . . . . . . . . . 210
Electrode Current . . . . . . . . . . . . . . . . . . . . . 210
Electrode Current Density . . . . . . . . . . . . . . . . . . 211
Electrode Power . . . . . . . . . . . . . . . . . . . . . . 211
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 211
Inlet . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
Outlet . . . . . . . . . . . . . . . . . . . . . . . . . . 212
Thin Gas Diffusion Electrode . . . . . . . . . . . . . . . . . 213
Thin Gas Diffusion Electrode Reaction. . . . . . . . . . . . . . 213

Theory for the Hydrogen Fuel Cell and Water Electrolyzer

Interfaces 214
Electronic Conducting Phase Theory . . . . . . . . . . . . . . 214
Electrolyte Phase Theory . . . . . . . . . . . . . . . . . . . 215
Gas Phase Theory . . . . . . . . . . . . . . . . . . . . . 215
Calculation of Built-in Equilibrium and Thermoneutral Potentials . . . . 217
References . . . . . . . . . . . . . . . . . . . . . . . . 220

Chapter 6: Chemical Species Transport Interfaces

The Transport of Diluted Species Interface 222

The Transport of Diluted Species in Porous Media Interface . . . . . 226
Domain, Boundary, and Pair Nodes for the Transport of Diluted
Species Interface. . . . . . . . . . . . . . . . . . . . . 228
Transport Properties . . . . . . . . . . . . . . . . . . . . 230

CONTENTS |9
 Turbulent Mixing . . . . . . . . . . . . . . . . . . . . . . 232
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 233
Mass-Based Concentrations . . . . . . . . . . . . . . . . . . 233
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 233
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 235
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 235
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 236
Concentration . . . . . . . . . . . . . . . . . . . . . . . 236
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 238
Flux Discontinuity . . . . . . . . . . . . . . . . . . . . . 238
Partition Condition . . . . . . . . . . . . . . . . . . . . . 239
Periodic Condition . . . . . . . . . . . . . . . . . . . . . 240
Line Mass Source . . . . . . . . . . . . . . . . . . . . . . 240
Point Mass Source . . . . . . . . . . . . . . . . . . . . . 241
Open Boundary . . . . . . . . . . . . . . . . . . . . . . 242
Thin Diffusion Barrier . . . . . . . . . . . . . . . . . . . . 242
Thin Impermeable Barrier . . . . . . . . . . . . . . . . . . 242
Equilibrium Reaction . . . . . . . . . . . . . . . . . . . . 243
Surface Reactions . . . . . . . . . . . . . . . . . . . . . 243
Surface Equilibrium Reaction . . . . . . . . . . . . . . . . . 244
Fast Irreversible Surface Reaction . . . . . . . . . . . . . . . 244
Porous Electrode Coupling . . . . . . . . . . . . . . . . . . 245
Reaction Coefficients . . . . . . . . . . . . . . . . . . . . 245
Electrode Surface Coupling . . . . . . . . . . . . . . . . . . 246
Porous Medium . . . . . . . . . . . . . . . . . . . . . . 246
Fluid . . . . . . . . . . . . . . . . . . . . . . . . . . 247
Porous Matrix . . . . . . . . . . . . . . . . . . . . . . . 249
Dispersion . . . . . . . . . . . . . . . . . . . . . . . . 249
Unsaturated Porous Medium . . . . . . . . . . . . . . . . . 250
Liquid . . . . . . . . . . . . . . . . . . . . . . . . . . 250
Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . 253
Volatilization . . . . . . . . . . . . . . . . . . . . . . . 255
Species Source. . . . . . . . . . . . . . . . . . . . . . . 256
Hygroscopic Swelling . . . . . . . . . . . . . . . . . . . . 256
Fracture . . . . . . . . . . . . . . . . . . . . . . . . . 257

10 | C O N T E N T S
The Transport of Diluted Species in Fractures Interface 258
Boundary, Edge, Point, and Pair Nodes for the Transport of Diluted
Species in Fractures Interface . . . . . . . . . . . . . . . . 260
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . 261
Concentration . . . . . . . . . . . . . . . . . . . . . . . 262
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
Fracture . . . . . . . . . . . . . . . . . . . . . . . . . 263
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 264
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 265
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 265
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 265
Species Source. . . . . . . . . . . . . . . . . . . . . . . 266

The Transport of Concentrated Species Interface 267

Domain, Boundary, and Pair Nodes for the Transport of
Concentrated Species Interface . . . . . . . . . . . . . . . 273
Transport Properties . . . . . . . . . . . . . . . . . . . . 274
Porous Media Transport Properties. . . . . . . . . . . . . . . 278
Electrode Surface Coupling . . . . . . . . . . . . . . . . . . 281
Turbulent Mixing . . . . . . . . . . . . . . . . . . . . . . 282
Reaction . . . . . . . . . . . . . . . . . . . . . . . . . 283
Reaction Sources . . . . . . . . . . . . . . . . . . . . . . 284
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 285
Mass Fraction . . . . . . . . . . . . . . . . . . . . . . . 286
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 288
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 289
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 289
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 289
Flux Discontinuity . . . . . . . . . . . . . . . . . . . . . 290
Open Boundary . . . . . . . . . . . . . . . . . . . . . . 290
Equilibrium Reaction . . . . . . . . . . . . . . . . . . . . 291
Surface Equilibrium Reaction . . . . . . . . . . . . . . . . . 292

The Chemistry Interface 293

Feature Nodes Available for the Chemistry Interface . . . . . . . . 297
Reaction . . . . . . . . . . . . . . . . . . . . . . . . . 297
Species . . . . . . . . . . . . . . . . . . . . . . . . . 302

CONTENTS | 11
 Electrode Reaction . . . . . . . . . . . . . . . . . . . . . 304
Electrode Reaction Group . . . . . . . . . . . . . . . . . . 307
Reversible Reaction Group . . . . . . . . . . . . . . . . . . 307
Equilibrium Reaction Group. . . . . . . . . . . . . . . . . . 309
Species Group . . . . . . . . . . . . . . . . . . . . . . . 310
Reaction Thermodynamics . . . . . . . . . . . . . . . . . . 310
Species Activity . . . . . . . . . . . . . . . . . . . . . . 311
Species Thermodynamics. . . . . . . . . . . . . . . . . . . 311

The Nernst-Planck-Poisson Equations Interface 312

The Electrophoretic Transport Interface 314

Common Settings for the Species Nodes in the Electrophoretic
Transport Interface . . . . . . . . . . . . . . . . . . . 317
Diffusion and Migration Settings . . . . . . . . . . . . . . . . 319
Domain, Boundary, and Pair Nodes for the Electrophoretic Transport
Interface. . . . . . . . . . . . . . . . . . . . . . . . 320
Solvent . . . . . . . . . . . . . . . . . . . . . . . . . 321
Porous Matrix Properties . . . . . . . . . . . . . . . . . . 321
Fully Dissociated Species . . . . . . . . . . . . . . . . . . . 321
Uncharged Species . . . . . . . . . . . . . . . . . . . . . 321
Weak Acid . . . . . . . . . . . . . . . . . . . . . . . . 322
Weak Base . . . . . . . . . . . . . . . . . . . . . . . . 322
Ampholyte . . . . . . . . . . . . . . . . . . . . . . . . 322
Protein . . . . . . . . . . . . . . . . . . . . . . . . . 323
Current Source . . . . . . . . . . . . . . . . . . . . . . 323
Initial Potential. . . . . . . . . . . . . . . . . . . . . . . 323
Current . . . . . . . . . . . . . . . . . . . . . . . . . 323
Current Density . . . . . . . . . . . . . . . . . . . . . . 323
Insulation . . . . . . . . . . . . . . . . . . . . . . . . . 324
Potential . . . . . . . . . . . . . . . . . . . . . . . . . 324
Species Source. . . . . . . . . . . . . . . . . . . . . . . 324
Initial Concentration . . . . . . . . . . . . . . . . . . . . 325
Concentration . . . . . . . . . . . . . . . . . . . . . . . 325
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 325
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 326
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 326

12 | C O N T E N T S
The Surface Reactions Interface 327
Boundary, Edge, Point, and Pair Nodes for the Surface Reactions
Interface. . . . . . . . . . . . . . . . . . . . . . . . 328
Surface Properties . . . . . . . . . . . . . . . . . . . . . 329
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 330
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 330
Surface Concentration . . . . . . . . . . . . . . . . . . . . 331

The Reacting Flow Interfaces 332

The Reacting Laminar Flow Interface . . . . . . . . . . . . . . 332
The Reacting Flow Coupling Feature . . . . . . . . . . . . . . 333
Physics Interface Features . . . . . . . . . . . . . . . . . . 335

The Reacting Flow in Porous Media Interfaces 337

The Reacting Flow in Porous Media, Transport of Diluted Species
Interface. . . . . . . . . . . . . . . . . . . . . . . . 337
The Reacting Flow in Porous Media, Transport of Concentrated
Species Interface. . . . . . . . . . . . . . . . . . . . . 338
The Reacting Flow, Diluted Species Coupling Feature . . . . . . . . 338
The Reacting Flow Coupling Feature . . . . . . . . . . . . . . 339
Physics Interface Features . . . . . . . . . . . . . . . . . . 339

Theory for the Transport of Diluted Species Interface 340

Mass Balance Equation . . . . . . . . . . . . . . . . . . . . 341
Equilibrium Reaction Theory . . . . . . . . . . . . . . . . . 342
Convective Term Formulation. . . . . . . . . . . . . . . . . 344
Solving a Diffusion Equation Only . . . . . . . . . . . . . . . 345
Mass Sources for Species Transport . . . . . . . . . . . . . . 345
Adding Transport Through Migration . . . . . . . . . . . . . . 347
Supporting Electrolytes . . . . . . . . . . . . . . . . . . . 348
Crosswind Diffusion . . . . . . . . . . . . . . . . . . . . 349
Danckwerts Inflow Boundary Condition . . . . . . . . . . . . . 350
Mass Balance Equation for Transport of Diluted Species in Porous
Media . . . . . . . . . . . . . . . . . . . . . . . . . 351
Convection in Porous Media . . . . . . . . . . . . . . . . . 352
Diffusion in Porous Media . . . . . . . . . . . . . . . . . . 354
Dispersion . . . . . . . . . . . . . . . . . . . . . . . . 355
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . 357

CONTENTS | 13
 Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 359
Mass Transport in Fractures . . . . . . . . . . . . . . . . . 360
References . . . . . . . . . . . . . . . . . . . . . . . . 361

Theory for the Transport of Concentrated Species Interface 363

Multicomponent Mass Transport . . . . . . . . . . . . . . . . 363
Multicomponent Gas Diffusion: Maxwell–Stefan Description . . . . . 364
Multicomponent Diffusivities . . . . . . . . . . . . . . . . . 366
Multicomponent Diffusion: Mixture-Averaged Approximation . . . . . 368
Multispecies Diffusion: Fick’s Law Approximation . . . . . . . . . 370
Multicomponent Thermal Diffusion . . . . . . . . . . . . . . . 371
Regularization of Reaction Rate Expression . . . . . . . . . . . . 371
References for the Transport of Concentrated Species Interface . . . . 372

Theory for the Electrophoretic Transport Interface 373

Theory for the Surface Reactions Interface 379

Governing Equations for the Surface Concentrations . . . . . . . . 379
Governing Equations for the Bulk Concentrations . . . . . . . . . 380
ODE Formulations for Surface Concentrations . . . . . . . . . . 382
Surface Reaction Equations on Deforming Geometries . . . . . . . 383
Reference for the Surface Reactions Interface . . . . . . . . . . . 384

Theory for the Coupling of Mass Transport to

Electrochemical Reactions 385
Molar Sources and Sinks . . . . . . . . . . . . . . . . . . . 385
Mass Sources and Sinks . . . . . . . . . . . . . . . . . . . 386

Theory for the Reacting Flow Interface 387

Pseudo Time Stepping for Mass Transport . . . . . . . . . . . . 387
The Stefan Velocity . . . . . . . . . . . . . . . . . . . . . 387
The Chemical Reaction Rate . . . . . . . . . . . . . . . . . 389

14 | C O N T E N T S
Chapter 7: Fluid Flow Interfaces

The Laminar Flow and Creeping Flow Interfaces 393

The Creeping Flow Interface . . . . . . . . . . . . . . . . . 393
The Laminar Flow Interface . . . . . . . . . . . . . . . . . . 394
Domain, Boundary, Pair, and Point Nodes for Single-Phase Flow . . . . . 399
Fluid Properties . . . . . . . . . . . . . . . . . . . . . . 399
Volume Force . . . . . . . . . . . . . . . . . . . . . . . 401
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 401
Wall . . . . . . . . . . . . . . . . . . . . . . . . . . 402
Inlet . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
Outlet . . . . . . . . . . . . . . . . . . . . . . . . . . 408
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 410
Open Boundary . . . . . . . . . . . . . . . . . . . . . . 410
Boundary Stress . . . . . . . . . . . . . . . . . . . . . . 411
Periodic Flow Condition . . . . . . . . . . . . . . . . . . . 412
Flow Continuity . . . . . . . . . . . . . . . . . . . . . . 413
Pressure Point Constraint . . . . . . . . . . . . . . . . . . 414
Point Mass Source . . . . . . . . . . . . . . . . . . . . . 414
Line Mass Source . . . . . . . . . . . . . . . . . . . . . . 415
Gravity . . . . . . . . . . . . . . . . . . . . . . . . . 416

The Darcy’s Law Interface 417

Domain, Boundary, Edge, Point, and Pair Nodes for the Darcy’s
Law Interface . . . . . . . . . . . . . . . . . . . . . . 419
Fluid and Matrix Properties . . . . . . . . . . . . . . . . . . 421
Mass Source . . . . . . . . . . . . . . . . . . . . . . . 424
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 424
Storage Model . . . . . . . . . . . . . . . . . . . . . . . 425
Richards’ Equation Model . . . . . . . . . . . . . . . . . . 426
Poroelastic Storage . . . . . . . . . . . . . . . . . . . . . 426
Gravity . . . . . . . . . . . . . . . . . . . . . . . . . 427
Porous Electrode Coupling . . . . . . . . . . . . . . . . . . 427
Electrode Surface Coupling . . . . . . . . . . . . . . . . . . 428
Pressure . . . . . . . . . . . . . . . . . . . . . . . . . 428
Mass Flux. . . . . . . . . . . . . . . . . . . . . . . . . 429
Line Mass Source . . . . . . . . . . . . . . . . . . . . . . 429

CONTENTS | 15
 Point Mass Source . . . . . . . . . . . . . . . . . . . . . 430
Inlet . . . . . . . . . . . . . . . . . . . . . . . . . . . 430
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 432
No Flow . . . . . . . . . . . . . . . . . . . . . . . . . 432
Flux Discontinuity . . . . . . . . . . . . . . . . . . . . . 432
Outlet . . . . . . . . . . . . . . . . . . . . . . . . . . 433
Precipitation . . . . . . . . . . . . . . . . . . . . . . . 433
Cross Section . . . . . . . . . . . . . . . . . . . . . . . 433
Thickness. . . . . . . . . . . . . . . . . . . . . . . . . 434
Interior Wall . . . . . . . . . . . . . . . . . . . . . . . 434
Thin Barrier. . . . . . . . . . . . . . . . . . . . . . . . 434
Pressure Head . . . . . . . . . . . . . . . . . . . . . . . 435
Hydraulic Head . . . . . . . . . . . . . . . . . . . . . . 435
Atmosphere/Gauge . . . . . . . . . . . . . . . . . . . . . 436
Pervious Layer . . . . . . . . . . . . . . . . . . . . . . . 436
Well . . . . . . . . . . . . . . . . . . . . . . . . . . 438
Fracture Flow . . . . . . . . . . . . . . . . . . . . . . . 438

The Free and Porous Media Flow Interface 439

Domain, Boundary, Point, and Pair Nodes for the Free and Porous
Media Flow Interface . . . . . . . . . . . . . . . . . . . 440
Fluid Properties . . . . . . . . . . . . . . . . . . . . . . 441
Fluid and Matrix Properties . . . . . . . . . . . . . . . . . . 442
Mass Source . . . . . . . . . . . . . . . . . . . . . . . 443
Volume Force . . . . . . . . . . . . . . . . . . . . . . . 443
Porous Electrode Coupling . . . . . . . . . . . . . . . . . . 444
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 444
Electrode-Electrolyte Interface Coupling . . . . . . . . . . . . . 444
Wall . . . . . . . . . . . . . . . . . . . . . . . . . . 445

The Brinkman Equations Interface 447

Domain, Boundary, Point, and Pair Nodes for the Brinkman
Equations Interface . . . . . . . . . . . . . . . . . . . . 449
Fluid and Matrix Properties . . . . . . . . . . . . . . . . . . 450
Mass Source . . . . . . . . . . . . . . . . . . . . . . . 452
Volume Force . . . . . . . . . . . . . . . . . . . . . . . 452
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 453
Fluid Properties . . . . . . . . . . . . . . . . . . . . . . 453

16 | C O N T E N T S
The Bubbly Flow Interface 455
The Laminar Bubbly Flow Interface . . . . . . . . . . . . . . . 455
Domain and Boundary Nodes for Bubbly Flow . . . . . . . . . . 458
Fluid Properties . . . . . . . . . . . . . . . . . . . . . . 459
Mass Transfer . . . . . . . . . . . . . . . . . . . . . . . 462
Gravity . . . . . . . . . . . . . . . . . . . . . . . . . 463
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 463
Wall . . . . . . . . . . . . . . . . . . . . . . . . . . 464
Inlet . . . . . . . . . . . . . . . . . . . . . . . . . . . 466
Outlet . . . . . . . . . . . . . . . . . . . . . . . . . . 467
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 469
Periodic Flow Condition . . . . . . . . . . . . . . . . . . . 469
Interior Wall . . . . . . . . . . . . . . . . . . . . . . . 470
Flow Continuity . . . . . . . . . . . . . . . . . . . . . . 471
Gas Boundary Condition Equations . . . . . . . . . . . . . . . 472

The Mixture Model Interface 473

The Mixture Model, Laminar Flow Interface. . . . . . . . . . . . 473
Domain and Boundary Nodes for the Mixture Model Interface . . . . 477
Mixture Properties . . . . . . . . . . . . . . . . . . . . . 478
Mass Transfer . . . . . . . . . . . . . . . . . . . . . . . 482
Gravity . . . . . . . . . . . . . . . . . . . . . . . . . 483
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 483
Wall . . . . . . . . . . . . . . . . . . . . . . . . . . 484
Inlet . . . . . . . . . . . . . . . . . . . . . . . . . . . 487
Outlet . . . . . . . . . . . . . . . . . . . . . . . . . . 488
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 490
Periodic Flow Condition . . . . . . . . . . . . . . . . . . . 490
Interior Wall . . . . . . . . . . . . . . . . . . . . . . . 491
Mixture Continuity . . . . . . . . . . . . . . . . . . . . . 492

The Euler-Euler Model Interface 493

The Euler-Euler Model, Laminar Flow Interface . . . . . . . . . . 493
Domain, Boundary, Point, and Pair Nodes for the Euler–Euler Model
Interfaces . . . . . . . . . . . . . . . . . . . . . . . 496
Phase Properties . . . . . . . . . . . . . . . . . . . . . . 497
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 501
Mass Transfer . . . . . . . . . . . . . . . . . . . . . . . 502

CONTENTS | 17
 Gravity . . . . . . . . . . . . . . . . . . . . . . . . . 502
Volume Force . . . . . . . . . . . . . . . . . . . . . . . 502
Wall . . . . . . . . . . . . . . . . . . . . . . . . . . 503
Inlet . . . . . . . . . . . . . . . . . . . . . . . . . . . 505
Outlet . . . . . . . . . . . . . . . . . . . . . . . . . . 506
Interior Wall . . . . . . . . . . . . . . . . . . . . . . . 507
Flow Continuity . . . . . . . . . . . . . . . . . . . . . . 508

Theory for the Laminar Flow and Creeping Flow Interfaces 510
General Single-Phase Flow Theory . . . . . . . . . . . . . . . 511
Compressible Flow . . . . . . . . . . . . . . . . . . . . . 513
Weakly Compressible Flow . . . . . . . . . . . . . . . . . . 513
The Mach Number Limit . . . . . . . . . . . . . . . . . . . 513
Incompressible Flow . . . . . . . . . . . . . . . . . . . . 514
The Reynolds Number. . . . . . . . . . . . . . . . . . . . 515
Theory for the Wall Boundary Condition . . . . . . . . . . . . 515
Prescribing Inlet and Outlet Conditions . . . . . . . . . . . . . 519
Mass Flow . . . . . . . . . . . . . . . . . . . . . . . . 520
Fully Developed Flow (Inlet) . . . . . . . . . . . . . . . . . 522
Fully Developed Flow (Outlet). . . . . . . . . . . . . . . . . 523
No Viscous Stress . . . . . . . . . . . . . . . . . . . . . 524
Normal Stress Boundary Condition . . . . . . . . . . . . . . . 525
Pressure Boundary Condition . . . . . . . . . . . . . . . . . 526
Mass Sources for Fluid Flow . . . . . . . . . . . . . . . . . 528
Numerical Stability — Stabilization Techniques for Fluid Flow . . . . . 530
Solvers for Laminar Flow . . . . . . . . . . . . . . . . . . . 532
Pseudo Time Stepping for Laminar Flow Models . . . . . . . . . . 534
Discontinuous Galerkin Formulation . . . . . . . . . . . . . . 536
Particle Tracing in Fluid Flow . . . . . . . . . . . . . . . . . 536
References for the Single-Phase Flow, Laminar Flow Interfaces . . . . 537

Theory for the Darcy’s Law Interface 540

About Darcy’s Law . . . . . . . . . . . . . . . . . . . . . 540
Darcy’s Law — Equation Formulation . . . . . . . . . . . . . . 541
Storage Model . . . . . . . . . . . . . . . . . . . . . . . 542
Average Linear Velocity . . . . . . . . . . . . . . . . . . . 543
References for the Darcy’s Law Interface. . . . . . . . . . . . . 543

18 | C O N T E N T S
 Theory for the Free and Porous Media Flow Interface 545
Reference for the Free and Porous Media Flow Interface. . . . . . . 545

Theory for the Brinkman Equations Interface 546

About the Brinkman Equations . . . . . . . . . . . . . . . . 546
Brinkman Equations Theory. . . . . . . . . . . . . . . . . . 546
References for the Brinkman Equations Interface. . . . . . . . . . 548

Theory for the Bubbly Flow Interface 549

The Bubbly Flow Equations . . . . . . . . . . . . . . . . . . 549
Turbulence Modeling in Bubbly Flow Applications . . . . . . . . . 553
References for the Bubbly Flow Interfaces . . . . . . . . . . . . 555

Theory for the Mixture Model Interface 556

The Mixture Model Equations . . . . . . . . . . . . . . . . . 556
Dispersed Phase Boundary Condition Equations . . . . . . . . . . 560
Turbulence Modeling in Mixture Models . . . . . . . . . . . . . 562
Slip Velocity Models. . . . . . . . . . . . . . . . . . . . . 563
References for the Mixture Model Interfaces . . . . . . . . . . . 565

Theory for the Euler-Euler Interface 566

The Euler–Euler Model Equations . . . . . . . . . . . . . . . 566
Some Notes on Boundary Conditions . . . . . . . . . . . . . . 576
Turbulent Two-Phase Flow Modeling . . . . . . . . . . . . . . 577
References for the Euler–Euler Model Interfaces . . . . . . . . . . 581

Theory for the Coupling of Fluid Flow to Electrochemical

Reactions 583
Momentum Sources and Sinks . . . . . . . . . . . . . . . . . . 583

Chapter 8: Heat Transfer Interfaces

Coupling of Heat Transfer to Electrochemical Reactions 586

Joule Heating Due to Charge Transport . . . . . . . . . . . . . 587
Heating Due to Electrochemical Reactions . . . . . . . . . . . . 587

CONTENTS | 19
 Chapter 9: Thermodynamics

Using Thermodynamic Properties 592

Workflow for Thermodynamics Property Calculations . . . . . . . 592
Thermodynamics . . . . . . . . . . . . . . . . . . . . . . 594
Thermodynamic System . . . . . . . . . . . . . . . . . . . 595
External Thermodynamic Packages . . . . . . . . . . . . . . . 603
External Thermodynamic System . . . . . . . . . . . . . . . . 604
Predefined System . . . . . . . . . . . . . . . . . . . . . 607
Exporting and Importing Thermodynamic Systems . . . . . . . . . 610
Species Property . . . . . . . . . . . . . . . . . . . . . . 610
Mixture Property. . . . . . . . . . . . . . . . . . . . . . 616
Equilibrium Calculation . . . . . . . . . . . . . . . . . . . 617
Generate Chemistry . . . . . . . . . . . . . . . . . . . . 621
Generate Material . . . . . . . . . . . . . . . . . . . . . 623
Coupling with the Reaction Engineering and the Chemistry Interfaces . . 627
Evaluating a Property Function in a Physics Interface . . . . . . . . 631
User-Defined Species . . . . . . . . . . . . . . . . . . . . 632
References . . . . . . . . . . . . . . . . . . . . . . . . 638

Thermodynamic Models and Theory 639

Introduction . . . . . . . . . . . . . . . . . . . . . . . 639
Thermodynamic Models . . . . . . . . . . . . . . . . . . . 639
Selecting the Right Thermodynamic Model . . . . . . . . . . . . 654
Species Property References . . . . . . . . . . . . . . . . . 656
Thermodynamic Properties Definitions . . . . . . . . . . . . . 657
Standard Enthalpy of Formation and Absolute Entropy Terms . . . . . 661
Reference State . . . . . . . . . . . . . . . . . . . . . . 662
Transport Properties . . . . . . . . . . . . . . . . . . . . 662
Surface Tension . . . . . . . . . . . . . . . . . . . . . . 687
References . . . . . . . . . . . . . . . . . . . . . . . . 688

Chapter 10: Multiphysics Coupling Nodes

Electrochemical Heating . . . . . . . . . . . . . . . . . . . 696
Potential Coupling . . . . . . . . . . . . . . . . . . . . . 696

20 | C O N T E N T S
 Space Charge Density Coupling . . . . . . . . . . . . . . . . 696
Reacting Flow, H2/O2 Gas Phase. . . . . . . . . . . . . . . . 697

Chapter 11: Glossary

Glossary of Terms 700

CONTENTS | 21
22 | C O N T E N T S
 1

Introduction

This guide describes the Fuel Cell & Electrolyzer Module, an optional add-on
package for COMSOL Multiphysics® designed to assist you in building detailed
models of the configuration of the electrodes and electrolyte in electrochemical
cells.

This chapter introduces you to the capabilities of the 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.

• About the Fuel Cell & Electrolyzer Module

• Overview of the User’s Guide

23
 About the Fuel Cell & Electrolyzer
Module
In this section:

• What Can the Fuel Cell & Electrolyzer Module Do?

• Fuel Cell & Electrolyzer Module Physics Interface Guide
• Common Physics Interface and Feature Settings and Nodes
• Where Do I Access the Documentation and Application Libraries?

What Can the Fuel Cell & Electrolyzer Module Do?

The Fuel Cell & Electrolyzer Module extends the COMSOL Multiphysics
environment with customized physics interfaces for modeling of fuel cells. These
physics interfaces provide tools for building detailed models of the configuration of the
electrodes and electrolyte in electrochemical cells. They include descriptions of the
electrochemical reactions and the transport properties that influence the performance
of fuel cells and other electrochemical cells. With this module, you have the perfect
tools to investigate the influence of using different materials, geometric configurations,
and operating conditions on the performance of a cell.

The physics interfaces include chemical species transport, current balances, heat
transfer, and fluid flow in electrochemical cells. You can use the module to investigate
the performance of fuel cells at different operating conditions for different electrode
configurations, structures and dimensions, for separators, current collectors and
current feeders, and for the choice of materials and chemistry.

The module adds the electrochemistry interfaces, which contains the Primary Current
Distribution, Secondary Current Distribution, and Tertiary Current Distribution,
Nernst-Planck interfaces. These are available for solid non-porous electrodes and for
porous electrodes. General tertiary current distribution models can also be set up using
the Chemical Species Transport interfaces. In addition to these generic physics
interfaces, the Electrochemistry branch contains dedicated Hydrogen Fuel Cell and
Water Electrolyzer interfaces.

24 | CHAPTER 1: INTRODUCTION
The tailored physics interfaces mentioned above are also complemented with extended
functionality in other physics interfaces for chemical species transport, heat transfer,
and fluid flow.

The physics interfaces for chemical species transport of neutral species are extended by
adding functionality that directly couple to electrochemical reactions defined in the
physics interfaces for electrochemical cells. A typical example is the transport and
reactions of gaseous species in gas diffusion electrodes and gas channels in fuel cells.

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

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

Finally, the Fuel Cell & Electrolyzer Module includes model examples of the following
electrochemical cells:

• Proton exchange membrane fuel cells (PEMFC)

• Solid oxide fuel cells (SOFC)
• Molten carbonate fuel cells (MCFC)
• Direct methanol fuel cells (DMFC)

See Where Do I Access the Documentation and Application Libraries? to locate and
use these examples and tutorials as a starting point to your own investigations.

Fuel Cell & Electrolyzer Module Physics Interface Guide

The table lists the physics interfaces available with this module in addition to the core
physics included with COMSOL Multiphysics.

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.

ABOUT THE FUEL CELL & ELECTROLYZER MODULE | 25

 PHYSICS INTERFACE ICON TAG SPACE AVAILABLE STUDY TYPE
DIMENSION

Chemical Species Transport

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

axisymmetric models only);
time dependent
Transport of Diluted tds all dimensions stationary; time dependent
Species
Transport of Diluted tds all dimensions stationary; time dependent
Species in Porous Media
Transport of Diluted dsf 3D, 2D, 2D stationary; time dependent
Species in Fractures axisymmetric
Electrophoretic Transport el all dimensions stationary; stationary with
initialization; time
dependent; time dependent
with initialization
Chemistry chem all dimensions stationary; time dependent

Transport of tcs all dimensions stationary; time dependent

Concentrated Species
Nernst-Planck-Poisson tds+es all dimensions stationary; time dependent;
Equations stationary source sweep;
small-signal analysis,
frequency domain
Reacting Flow

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

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

Reacting Flow in Porous Media

Transport of Diluted rfds 3D, 2D, 2D stationary; time dependent

Species axisymmetric
Transport of rfcs 3D, 2D, 2D stationary; time dependent
Concentrated Species axisymmetric

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

Electrochemistry

Primary Current cd all dimensions stationary; stationary with

Distribution initialization; time
dependent; time dependent
with initialization; AC
Secondary Current
impedance, initial values;
Distribution
AC impedance, stationary;
AC impedance, time
dependent
Tertiary Current tcd all dimensions stationary; stationary with
Distribution, initialization; time
Nernst-Planck dependent; time dependent
(Electroneutrality, with initialization; AC
Water-Based with impedance, initial values;
Electroneutrality, AC impedance, stationary;
Supporting Electrolyte) AC impedance, time
dependent
Electroanalysis 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
Hydrogen Fuel Cell fc all dimensions stationary; time dependent;
Interfaces frequency domain
Water Electrolyzer fc all dimensions stationary; time dependent;
Interfaces frequency domain
Fluid Flow

Multiphase Flow

Bubbly Flow

Laminar Bubbly Flow bf 3D, 2D, 2D stationary; time dependent

axisymmetric

ABOUT THE FUEL CELL & ELECTROLYZER MODULE | 27

 PHYSICS INTERFACE ICON TAG SPACE AVAILABLE STUDY TYPE
DIMENSION

Mixture Model

Mixture Model, mm 3D, 2D, 2D stationary; time dependent

Laminar Flow axisymmetric
Euler-Euler Model

Euler-Euler Model, ee 3D, 2D, 2D stationary; time dependent

Laminar Flow axisymmetric
Phase Transport Mixture Model

Phase Transport, — 3D, 2D, 2D stationary; time dependent

Mixture Model, axisymmetric
Laminar Flow
Phase Transport

Phase Transport phtr 3D, 2D, 2D stationary; time dependent

axisymmetric
Phase Transport in phtr 3D, 2D, 2D stationary; time dependent
Porous Media axisymmetric
Porous Media and Subsurface Flow

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

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

Multiphase Flow in — 3D, 2D, 2D stationary; time dependent

Porous Media axisymmetric
Free and Porous Media fp 3D, 2D, 2D stationary; time dependent
Flow axisymmetric
Heat Transfer

Heat Transfer in Porous ht all dimensions stationary; time dependent

Media

28 | CHAPTER 1: INTRODUCTION
Common Physics Interface and Feature Settings and Nodes
There are several common settings and sections available for the physics interfaces and
feature nodes. Some of these sections also have similar settings or are implemented in
the same way no matter the physics interface or feature being used. There are also some
physics feature nodes that display in COMSOL Multiphysics.

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

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

In the COMSOL Multiphysics Reference Manual see Table 2-4 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

ABOUT THE FUEL CELL & ELECTROLYZER MODULE | 29

 to highlight a node or window, then press F1 to open the Help window, which then
displays information about that feature (or click a node in the Model Builder followed
by the Help button ( ). This is called topic-based (or context) help.

Opening the Documentation Window

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.

Opening the Application Libraries Window

To open the Application Libraries window ( ):

CONTACTING COMSOL BY EMAIL

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

COMSOL ACCESS AND TECHNICAL SUPPORT

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

30 | CHAPTER 1: INTRODUCTION
COMSOL ONLINE RESOURCES

COMSOL website www.comsol.com

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

ABOUT THE FUEL CELL & ELECTROLYZER MODULE | 31

 Overview of the User’s Guide
The Fuel Cell & Electrolyzer 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.

THE ELECTROCHEMISTRY INTERFACES

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

THE FUEL CELL AND WATER ELECTROLYZER INTERFACES

The Fuel Cell and Electrolyzer Interfaces chapter describes the Hydrogen Fuel Cell
and the Water Electrolyzer interfaces as well as the underlying theory for these
interfaces.

THE CHEMICAL SPECIES TRANSPORT INTERFACES

The Chemical Species Transport Interfaces chapter describes the Transport of Diluted
Species, Transport of Concentrated Species, the Transport of Diluted Species in
Porous Media, and the Surface Reaction interfaces. The rest of the chapter describes
these interfaces in detail as well as the underlying theory.

32 | CHAPTER 1: INTRODUCTION
Theory for the Transport of Diluted Species Interface section describes the Reacting
Flow in Porous Media (rfcs) and Reacting Flow in Porous Media (rfds) interfaces
including its underlying theory.

THE FLUID FLOW INTERFACES

The Fluid Flow Interfaces chapter describes the Darcy’s Law and Free and Porous
Media Flow interfaces, both included under the Porous Media and Subsurface Flow
branch. The Laminar Flow interface is also available and is described in the COMSOL
Multiphysics Reference Manual.

THE HEAT TRANSFER INTERFACES

The Heat Transfer Interfaces chapter describes how to couple electrochemical heat
sources to heat transfer.

THE MULTIPHYSICS COUPLING NODES

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

OVERVIEW OF THE USER’S GUIDE | 33

34 | CHAPTER 1: INTRODUCTION
 2

Modeling with Electrochemistry

In this chapter:
• Introduction to Electrochemistry Modeling

35
 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
• Aspects to Consider When Modeling Batteries or Fuel Cells
• Modeling Cyclic Voltammetry
• Common Simplifications When Modeling Electrochemical Cells
• Before You Start Building Your Model
• Meshing Advice
• Solving Electrochemical Models
• Postprocessing Your Solution

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

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

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

36 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

Electrochemical Applications
Electrochemical systems may be classified in different ways.

One approach is to contrast those electrochemical systems involving desirable reactions

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

Corrosion is an example of undesirable electrochemistry because in this case

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

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

The different electrochemical modules in COMSOL Multiphysics are designed to

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

Fundamentals of Electrochemistry Modeling

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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 37

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

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

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

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

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

anode, at which the electrochemical reaction transfers electrons from electrolyte to
electrode, and a cathode, at which electrons are 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

38 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

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

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

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

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

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

Polarization curves are frequently nonlinear. The combination of nonlinearity and

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

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

Current Distribution Cases and Choosing the Right Interface to

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

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

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

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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 39

 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

40 | 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 = v

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

D =  0  s E = –  0  s V

Hence

2 v
 V + ---------- = 0
0 s

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

v = F  zi ci
i

Hence

F
0 s 
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  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 | 41

 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  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  0  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

42 | 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 – --------  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 = –  l  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 l is given as:

2
F
 zi
2
 l = -------- Di ci
RT

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 43

 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
 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 l 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.

44 | 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:

G 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 (G = 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

G = – 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 | 45

 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   --------   s –  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

 m =  s –  l – E eq m

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

interface.

 m depends on both the electric potential in the electrode  s and the

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

46 | 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  ---- = A
i
 i 0

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:

 a F –  c F
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 | 47

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

  a +  c F
i loc = i 0  ---------------------------- 
 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:

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

48 | 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  a FE  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 = s – l (2-3)

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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 49

 a + c = 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:

 a F  c F
i loc = i 0  exp  --------------- – exp  – --------------  (2-5)
  RT   RT  

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

  n a  n
i 0 = i 0 0 c Rc cO (2-6)

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

The overpotential is here defined as

 = E – E eq (2-7)

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

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

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

Note that in Equation 2-5 both i0 and Eeq are concentration dependent. This has some
numerical drawbacks when modeling electrochemical cells including mass transport,
since for low concentrations of the participating species (that is, when c O  0 or
cR
c 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

cR  a F ref cO  c F ref
i loc = i 0 ref  ------------- exp  -------------------- – -------------- exp  – -------------------  (2-9)
 c R ref  RT  c O ref  RT  

where

50 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

  n  n
i 0 ref = i 0 0 c Rc ref c Oa ref (2-10)

and

 ref = E – E eq,ref (2-11)

with

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

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

Double Layer Capacitance

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

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

This effect can be added to via the Double Layer Capacitance condition. The capacitor
stores a surface charge density Q = C d   s –  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 | 51

 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

52 | 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 | 53

 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

Aspects to Consider When Modeling Batteries or Fuel Cells

Batteries and fuel cells are electrochemical energy extraction devices that work by using
a conducting domain to separate two regions, where the two halves of an overall
favorable chemical reaction proceed. By preventing the mixing of reactants and instead
forcing the reaction to proceed by mediation of electrical current between the
separated reactants, energy can be extracted as a voltage.

In a battery, there is a finite supply of reactant and the system is closed. In a fuel cell,
by contrast, there is a continuous feed of reactant to the system. A battery can be
simpler since it involves a single closed system, but a fuel cell may have other
advantages such as decreasing overall weight since it separates the site of energy storage
from that of energy extraction.

A battery does not have a steady state condition since its feedstock of reactants
progressively depletes until it is consumed. Once consumed, the battery is discharged
and it will no longer provide a voltage as its source of electrochemical energy has run
out. In a rechargeable battery, the process is reversible and the application of a voltage
can return the battery to saturation with feedstock under charging.

The electrochemistry in a battery model usually does not have a steady

state, and so it is not appropriate to use a Stationary study with a battery
interface.

Fuel cells do have steady states, although transient effects may also be important in fuel
cell research. In a fuel cell, it is typically important to identify what features of the
system may be rate-limiting for the steady-state current: the transport of reactants to

54 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

the electrodes, the electrode kinetics themselves and the transport of current through
the electrolyte may all cause bottlenecks.

The maximum achievable voltage in a battery or fuel cell is the difference between the
half-cell potentials. The discharge mode is the direction in which the overall reaction
is thermodynamically downhill (negative G).

There can be variation in the literature between whether the charge or

discharge mode is assumed when an electrode in a battery is referred to as
the “anode” or “cathode”. Each electrode can operate in both roles,
depending on whether the battery is charging or discharging.

Typically a battery model can be set up using Secondary Current Distribution to describe
charge transport since the long charge and discharge times ensure that conductivities
remain relatively uniform through the cell. If coupling to species transport is required,
Transport of Diluted Species can be added with an Electrode Reaction Coupling condition.

PREDEFINED BATTERY INTERFACES

Certain common battery types have predefined physics interfaces. Common for all
these interfaces is that by the use of concentrated electrolyte theory for the charge and
mass transport in the electrolyte, a more accurate electrolyte transport model is
achieved, compared to the Nernst-Planck equations described earlier in this chapter.

Lithium-Ion Battery is used for solving problems in batteries where the anode (in
discharge mode) is lithium metal intercalated into a material such as graphite, and the
cathode (in discharge mode) is lithium ions intercalated into a transition metal oxide.
The electrical current through the electrolyte is carried by lithium ions, typically in an
organic solution. Because both the anode and cathode materials are typically porous to
maximize the active surface area, the Porous Electrode domain node is standard do
define each electrode.

The Battery with Binary Electrolyte interface can be used for a range of general battery
types involving porous electrodes and current transfer through an ionic conductor. An
example is the nickel-metal hydride battery — an early type of rechargeable battery in
which the discharge anode is a metal hydride, the discharge cathode is a hydrated nickel
oxide, and the current is transferred by high concentration potassium hydroxide in
aqueous solution.

The Lead-Acid Battery interface is designed for batteries in which the discharge process
is the conproportionation of Pb(0) and Pb(IV) through a sulfuric acid medium.

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 55

 FUEL CELL MODELING
Fuel cell modeling is complex since it is a closely coupled multiphysics problem
involving charge, mass and momentum conservation. These physics are normally set
up by coupling Secondary Current Distribution for the charge transfer, Transport of
Concentrated Species for gas phase mass transport, and Free and Porous Media Flow for
momentum transport (fluid flow) in the porous gas diffusion layers and the free flow
gas channels. The latter is a combination of Laminar Flow for free flow and Brinkman
Equations for porous flow.

In a fuel cell, any one of electrochemical reactivity, mass transport of reactants to either
electrode, and electrical resistance can cause a “bottleneck”, limiting the current drawn
for a given voltage. An accurate study of the polarization curve of a fuel cell must
therefore incorporate all of the physical effects to identify the voltages at which the fuel
cell behavior varies from transport-limited to being limited by the kinetics of the
electrolysis reaction.

When setting up a fuel cell study, it is a good idea to include physics

interfaces one at a time. In particular, make sure that Fluid Flow physics
interfaces are correctly set up before proceeding to incorporate species
transport. See also Solving Electrochemical Models below.

• The Transport of Concentrated Species Interface

• The Free and Porous Media Flow Interface
• The Primary and Secondary Current Distribution InterfacesThe
Primary and Secondary Current Distribution Interfaces

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.

56 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

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.

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”.

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 57

 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
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

58 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

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
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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 59

 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?

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

60 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

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

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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 61

 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).
• 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

62 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

 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
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.

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 63

 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
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.

64 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

 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

Postprocessing Your Solution

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

VARIABLE DESCRIPTION DEFINED AT

phil Electrolyte phase potential Electrolyte and Porous

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

The unit is V for all the above variables.

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

CURRENT VARIABLES AND CALCULATING THE TOTAL CELL CURRENT

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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 65

 To calculate the total current in COMSOL Multiphysics, it is necessary to integrate the
total drawn current density along the boundary or over the domain of the electrode.
Some common current density variables are shown in Table 2-2.
TABLE 2-2: COMMON CURRENT DENSITY VARIABLES.

VARIABLE UNIT DESCRIPTION DEFINED AT

2
xxx.nIl A/m Electrolyte current density in Boundaries to Electrolyte and
normal direction Porous Electrode domains
xxx.nIs A/m2 Electrode current density in Boundaries to Electrolyte and
normal direction Porous Electrode domains
xxx.iloc_yy A/m2 Local current density of Electrode Reaction boundaries
electrode reaction
xxx.itot A/m2 Total interface current density Electrode Reaction boundaries
(local sum of all xxx.iloc_yy)
xxx.iv_yy A/m3 Volumetric current density of a Porous Electrode domains
Porous Electrode Reaction
xxx.ivtot A/m3 Total volumetric current Porous Electrode domains
densities (local sum of all
xxx.iv_yy)
xxx.IlMag A/m2 Electrolyte current density Electrolyte domains
magnitude (L2 norm)
xxx.IsMag A/m2 Electrode current density Electrode domains
magnitude (L2 norm)

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

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

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

You can also define your own total current variable by using an Integration nonlocal
coupling across the electroactive boundaries. This variable can also be used during the

66 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

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 xxx.IlMag/xxx.IsMag variables on boundaries. These

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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 67

68 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY
 3

AC/DC Interfaces

This chapter describes the physics interfaces found under the AC/DC branch .

In this chapter:

• The Electrostatics Interface

• The Electric Currents Interface
• Theory for the Electrostatics Interface
• Theory for the Electric Currents Interface
See the COMSOL Multiphysics Reference Manual for details about The Magnetic
Fields Interface and the Theory of Magnetic Fields.

69
 The Electrostatics Interface
The Electrostatics (es) interface ( ), found under the AC/DC>Electric Fields and
Currents branch when adding a physics interface, is used to compute the electric field,
electric displacement field, and potential distributions in dielectrics under conditions
where the electric charge distribution is explicitly prescribed. The formulation is
stationary except for use together with other physics interfaces. Eigenfrequency,
frequency-domain, small-signal analysis, and time-domain modeling are supported in
all space dimensions.

The physics interface solves Gauss’ law for the electric field using the scalar electric
potential as the dependent variable.

Charge Conservation is the main node, which adds the equation for the electric
potential and has a Settings window for defining the constitutive relation for the
electric displacement field and its associated properties such as the relative permittivity.

When this physics interface is added, these default nodes are also added to the Model
Builder — Charge Conservation, Zero Charge (the default boundary condition), and
Initial Values. Then, from the Physics toolbar, add other nodes that implement, for
example, boundary conditions and space charges. You can also right-click Electrostatics
to select physics features from the context menu.

Physics-Controlled Mesh
The physics-controlled mesh is controlled from the Mesh node’s Settings window (if the
Sequence type is Physics-controlled mesh). There, in the table in the Physics-Controlled
Mesh section, find the physics interface in the Contributor column and select or clear
the check box in the Use column on the same table row for enabling (the default) or
disabling contributions from the physics interface to the physics-controlled mesh.

Information from the physics, such as the presence of an infinite elements domain or
periodic condition, will be used to automatically set up an appropriate meshing
sequence.

In the COMSOL Multiphysics Reference Manual see the

Physics-Controlled Mesh section for more information about how to
define the physics-controlled mesh.

70 | CHAPTER 3: AC/DC INTERFACES

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 es.

CROSS-SECTION AREA (1D COMPONENTS)

For 1D components, enter a default value for the Cross-section area A (SI unit: m2).
The default value of 1 is typically not representative for a thin domain. Instead it
describes a unit thickness that makes the 1D equation identical to the equation used
for 3D components. See also Change Cross Section.

THICKNESS (2D COMPONENTS)

For 2D components, enter a default value for the Out-of-plane thickness d (SI unit: m).
The default value of 1 is typically not representative for a thin dielectric medium, for
example. Instead it describes a unit thickness that makes the 2D equation identical to
the equation used for 3D components. See also Change Thickness (Out-of-Plane).

DEPENDENT VARIABLES
The dependent variable is the Electric potential V. You can change its name, which
changes both the field name and the variable name. If the new name coincides with the
name of another electric potential field in the model, the physics interfaces shares
degrees of freedom. The new name must not coincide with the name of a field of
another type or with a component name belonging to some other field.

DISCRETIZATION
Select the shape order for the Electric potential dependent variable — Linear, Quadratic
(the default), Cubic, Quartic, or Quintic. For more information about the Discretization

THE ELECTROSTATICS INTERFACE | 71

 section, see Settings for the Discretization Sections 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.

Electric Sensor: Application Library path COMSOL_Multiphysics/

Electromagnetics/electric_sensor

Domain, Boundary, Edge, Point, and Pair Nodes for the

Electrostatics Interface
The Electrostatics interface has these domain, boundary, edge, point, and pair nodes
available.

ABOUT THE BOUNDARY CONDITIONS

The relevant physics interface condition at interfaces between different media is

n2   D1 – D2  = s

In the absence of surface charges, this condition is fulfilled by the natural boundary
condition

n     0 V – P  1 –   0 V – P  2  = – n   D 1 – D 2  = 0

AVAILABLE NODES
These nodes, listed in alphabetical order, 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). Also see Table 3-1 for a list of interior and exterior
boundary conditions, including edge, point, and pair availability.

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.

72 | CHAPTER 3: AC/DC INTERFACES

• Change Cross Section • Line Charge (on Axis)
• Change Thickness (Out-of-Plane) • Line Charge (Out-of-Plane)
• Charge Conservation • Periodic Condition
1,2
• Charge Conservation, Piezoelectric • Point Charge
• Conduction Loss (Time-Harmonic) • Point Charge (on Axis)
• Electric Displacement Field • Space Charge Density
• Electric Potential • Surface Charge Density
• External Surface Charge Accumulation • Thin Low Permittivity Gap
• Zero Charge (the default boundary
condition)
1
This feature is available with the Piezoelectricity multiphysics interface.
2
Rrequires the Acoustics Module, MEMS Module, or the Structural Mechanics
Module.

THE ELECTROSTATICS INTERFACE | 73

 Table 3-1 lists the interior and exterior boundary conditions available with this physics
interface. It also includes edge, point, and pair availability.
TABLE 3-1: INTERIOR AND EXTERIOR BOUNDARY CONDITIONS (INCLUDING EDGE, POINT, AND PAIR
AVAILABILITY) FOR THE ELECTROSTATICS INTERFACE

NODE INTERIOR EXTERIOR ALSO AVAILABLE FOR

Change Cross Section x x pairs

Change Thickness (Out-of-Plane) x x pairs
Electric Displacement Field x x pairs
Electric Potential x x edges, points, and pairs
External Surface Charge x pairs
Accumulation
Ground x x edges, points, and pairs
Periodic Condition x not applicable
Surface Charge Density x x pairs
Thin Low Permittivity Gap x not applicable
Zero Charge (the default) x x pairs

For axisymmetric components, COMSOL Multiphysics takes the axial

symmetry boundaries (at r = 0) into account and automatically adds an
Axial Symmetry node to the model that is valid on the axial symmetry
boundaries only. There are also Line Charge (on Axis) and Point Charge (on
Axis) available.

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.

Charge Conservation
The Charge Conservation node adds the equations for charge conservation according to
Gauss’ law for the electric displacement field. It provides an interface for defining the
constitutive relation and its associated properties such as the relative permittivity.

74 | CHAPTER 3: AC/DC INTERFACES

MATERIAL TYPE
The Material type setting decides how materials behave and how material properties are
interpreted when the mesh is deformed. Select Solid for materials whose properties
change as functions of material strain, material orientation, and other variables
evaluated in a material reference configuration (material frame). Select Nonsolid for
materials whose properties are defined only as functions of the current local state at
each point in the spatial frame, and for which no unique material reference
configuration can be defined. Select From material to pick up the corresponding setting
from the domain material on each domain.

CONSTITUTIVE RELATION D-E

Select a Dielectric model to describe the macroscopic properties of the medium
(relating the electric displacement D with the electric field E) and the applicable
material properties, such as the relative permittivity. Select:

• Relative permittivity (the default) to use the constitutive relation D0rE. Then
the default is to take the Relative permittivity r (dimensionless) values From material.
For User defined, select Isotropic, Diagonal, Symmetric, or Full and enter values or
expressions in the field or matrix. The default is 1.
• Polarization to use the constitutive relation D0E  P. Then enter the components
based on space dimension for the Polarization vector P (SI unit: C/m2). The
defaults are 0 C/m2.
• Remanent electric displacement to use constitutive relation D0rE  Dr, where Dr
is the remanent displacement (the displacement when no electric field is present).
Then the default is to take the Relative permittivity r (dimensionless) values From
material. For User defined, select Isotropic, Diagonal, Symmetric, or Full and enter
values or expressions in the field or matrix. Then enter the components based on
space dimension for the Remanent electric displacement Dr (SI unit: C/m2). The
defaults are 0 C/m2.

Conduction Loss (Time-Harmonic)

This feature requires the Acoustics Module, MEMS Module, or the

Structural Mechanics Module. See the individual documentation for
information.

THE ELECTROSTATICS INTERFACE | 75

 The Conduction Loss (Time-Harmonic) subnode allows you to model possible conductive
losses in a dielectric material. The effect is only active in a Eigenfrequency or Frequency
response study.

CONDUCTION CURRENT
By default, the Electrical conductivity  for the media is defined From material. You can
also select User defined or Linearized resistivity.

• For User defined select Isotropic, Diagonal, Symmetric, or Full depending on the
characteristics of the electrical conductivity, and then enter values or expressions for
the Electrical conductivity  in the field or matrix.
• For Linearized resistivity the default Reference temperature Tref, and Resistivity
temperature coefficient , and Reference resistivity 0 are taken From material, which
means that the values are taken from the domain (or boundary) material. T is the
current temperature, which can be a value that is specified as a model input or the
temperature from a heat transfer interface. The definition of the temperature field
appears in the Model Inputs section.

LOCATION IN USER INTERFACE

Context Menus
Electrostatics>Charge Conservation>Conduction Loss (Time-Harmonic)

Ribbon
Physics tab with Charge Conservation node selected in the model tree:

Attributes>Conduction Loss (Time-Harmonic)

Initial Values
The Initial Values node adds an initial value for the electric potential V that can serve
as an initial condition for a transient simulation or as an initial guess for a nonlinear
solver.

INITIAL VALUES
Enter a value or expression for the initial value of the Electric potential V (SI unit: V).
The default value is 0 V.

76 | CHAPTER 3: AC/DC INTERFACES

Space Charge Density
The Space Charge Density node adds a space charge density , which appears on the
right-hand side of the equation that the physics interface defines.

SPACE CHARGE DENSITY

Enter a value or expression for the Space charge density v(SI unit: C/m3). The default
is 0 C/m3.

Zero Charge
The Zero Charge node adds the condition that there is zero charge on the boundary so
that n D  0. This boundary condition is also applicable at symmetry boundaries
where the potential is known to be symmetric with respect to the boundary. This is the
default boundary condition at exterior boundaries. At interior boundaries, it means
that no displacement field can penetrate the boundary and that the electric potential is
discontinuous across the boundary.

Ground
The Ground node implements ground (zero potential) as the boundary condition
V = 0.

Ground means that there is a zero potential on the boundary. This boundary condition
is also applicable at symmetry boundaries where the potential is known to be
antisymmetric with respect to the boundary.

For some physics interfaces, also select additional Ground nodes from the Edges (3D
components) or Points (2D and 3D components) submenus. For 2D axisymmetric
components, it can be applied on the Symmetry axis.

BOUNDARY, 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.

THE ELECTROSTATICS INTERFACE | 77

 Electric Potential
The Electric Potential node provides an electric potential V0 as the boundary condition
V = V0.

Because the electric potential is being solved for in the physics interface, the value of
the potential is typically defined at some part of the geometry. For some physics
interfaces, also select additional Electric Potential nodes from the Edges (3D
components) or Points (2D and 3D components) submenus. For 2D axisymmetric
components, it can be applied on the symmetry axis.

BOUNDARY, 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 V0 (SI unit: V). The default is
0 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.

Surface Charge Density

The Surface Charge Density node provides the following surface-charge boundary
condition for exterior boundaries (left) and interior boundaries (right):

–n  D = s , n   D1 – D2  = s

Specify the surface charge density s at an outer boundary or at an interior boundary

between two nonconducting media.

Add a contribution as a Harmonic Perturbation by right-clicking the parent node or

click Harmonic Perturbation on the Physics toolbar. For more information, see
Harmonic Perturbation — Exclusive and Contributing Nodes.

SURFACE CHARGE DENSITY

Enter the value or expression for the Surface charge density s (SI unit: C/m2).

78 | CHAPTER 3: AC/DC INTERFACES

External Surface Charge Accumulation
The External Surface Charge Accumulation node implements the boundary condition

–n  D = s

where s is the solution of the following distributed ODE on the boundary:

d s
= n  Ji + n  Je
dt

where n·Ji is the normal component of the total ion current density on the wall and
n·Je is the normal component of the total electron current density on the wall, which
are feature inputs.

MATERIAL TYPE
The Material type setting decides how materials behave and how material properties are
interpreted when the mesh is deformed. Select Solid for materials whose properties
change as functions of material strain, material orientation, and other variables
evaluated in a material reference configuration (material frame). Select Nonsolid for
materials whose properties are defined only as functions of the current local state at
each point in the spatial frame, and for which no unique material reference
configuration can be defined. Select From material to pick up the corresponding setting
from the domain material on each domain.

EXTERNAL SURFACE CHARGE ACCUMULATION

Enter values or expressions for the Normal ion current density n·Ji (SI unit: A/m2)
and the Normal electron current density n·Je (SI unit: A/m2).

Electric Displacement Field

The Electric Displacement Field node adds the following electric-displacement
boundary condition:

n  D = n  D0

It specifies the normal component of the electric displacement field at a boundary.

ELECTRIC DISPLACEMENT FIELD

Enter the coordinates of the Boundary electric displacement field D0 (SI unit: C/m2).

THE ELECTROSTATICS INTERFACE | 79

 Periodic Condition
The Periodic Condition node defines periodicity or antiperiodicity between two
boundaries. If required, activate periodic conditions on more than two boundaries, in
which case the Periodic Condition tries to identify two separate surfaces that can each
consist of several connected boundaries. For more complex geometries, it might be
necessary to use the Destination Selection subnode. With this subnode the boundaries
which constitute the source and destination surfaces can be manually specified. The
Destination Selection subnode is available from the context menu (right-click the parent
node) as well as from the Physics toolbar, Attributes menu.

When this feature is used in conjunction with a feature on connected

boundaries, wherever the sector symmetry boundaries connect with the
periodic boundaries, the same periodic condition feature cannot be used
on both sides. At least two periodic condition features are required for the
model to compute correctly.

BOUNDARY SELECTION
When using nonconforming meshes on the source and destination of a periodic
boundary pair, for numerical stability, a finer mesh should be applied on the
destination side. Use conforming meshes if possible.

PERIODIC CONDITION
Select a Type of periodicity — Continuity (the default), Antiperiodicity, or Floquet
periodicity. Select:

• Continuity to make the electric potential periodic (equal on the source and
destination).
• Antiperiodicity to make it antiperiodic.
• Floquet periodicity (only available with products supporting piezoelectric modeling).
Specify the components of the k-vector for Floquet periodicity kF (SI unit: rad/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.

For information about the Orientation of Source section, see Orientation of Source
and Destination.

80 | CHAPTER 3: AC/DC INTERFACES

Thin Low Permittivity Gap
Use the Thin Low Permittivity Gap node

0 r
n  D 1 = ----------  V 1 – V 2 
d
0 r
n  D 2 = ----------  V 2 – V 1 
d

to model a thin gap of a material with a small permittivity compared to the adjacent
domains. The layer has the thickness d and the relative permittivity r. The indices 1
and 2 refer to the two sides of the boundary.

THIN LOW PERMITTIVITY GAP

The default is to take the Relative permittivity r (dimensionless) values From material.
For User defined, enter a different value or expression. Enter a Thickness d (SI unit: m).
The default is 5 mm.

Line Charge
For 3D components, use the Line Charge node to specify line charges along the edges
of a geometry. Add a contribution as a Harmonic Perturbation by right-clicking the
parent node or clicking Harmonic Perturbation on the Physics toolbar. For more
information see Harmonic Perturbation — Exclusive and Contributing Nodes.

EDGE SELECTION

Beware that constraining the potential on edges usually yields a current

outflow that is mesh dependent.

LINE CHARGE
Enter a value or expression to apply a Line charge QL (SI unit: C/m). This source
represents electric charge per unit length and the default is 0 C/m.

Line Charge (on Axis) and Line Charge (Out-of-Plane)

THE ELECTROSTATICS INTERFACE | 81

 Line Charge (on Axis)
For 2D axisymmetric components, use the Line Charge (on Axis) node to specify line
charges along the symmetry axis.

Add a contribution as a Harmonic Perturbation by right-clicking the parent node or

click Harmonic Perturbation on the Physics toolbar. For more information see
Harmonic Perturbation — Exclusive and Contributing Nodes.

LINE CHARGE (ON AXIS)

Enter a value or expression to apply a Line charge QL (SI unit: C/m). This source
represents electric charge per unit length and the default is 0 C/m.

Line Charge and Line Charge (Out-of-Plane)

Line Charge (Out-of-Plane)

For 2D and 2D axisymmetric components, points are selected and this is the same as
a line out-of-plane.

Add a contribution as a Harmonic Perturbation by right-clicking the parent node or

clicking Harmonic Perturbation on the Physics toolbar. For more information see
Harmonic Perturbation — Exclusive and Contributing Nodes.

Use the Line Charge (Out-of-Plane) node to specify line charges along the points of a
geometry for 2D and 2D axisymmetric components.

POINT SELECTION

Beware that constraining the potential on points usually yields a current

outflow that is mesh dependent.

82 | CHAPTER 3: AC/DC INTERFACES

LINE CHARGE (OUT-OF-PLANE)
Enter a value or expression to apply a Line charge QL (SI unit: C/m). This source
represents electric charge per unit length and the default is 0 C/m.

Line Charge and Line Charge (on Axis)

Point Charge
The Point Charge node adds a point source to 3D components. The point charge
represents an electric displacement field flowing out of the point.

Add a contribution as a Harmonic Perturbation by right-clicking the parent node or

clicking Harmonic Perturbation on the Physics toolbar. For more information see
Harmonic Perturbation — Exclusive and Contributing Nodes.

POINT SELECTION

Beware that constraining the potential on points usually yields a current

outflow that is mesh dependent.

POINT CHARGE
Enter a value or expression to apply a Point charge QP (SI unit: C) to points. This
source represents an electric displacement field flowing out of the point. The default is
0 C.

Point Charge (on Axis) and Line Charge (Out-of-Plane)

Point Charge (on Axis)

The Point Charge (on Axis) node adds a point source to 2D axisymmetric components.
The point charge represents an electric displacement field flowing out of the point.

Add a contribution as a Harmonic Perturbation by right-clicking the parent node or

clicking Harmonic Perturbation on the Physics toolbar. For more information see
Harmonic Perturbation — Exclusive and Contributing Nodes.

THE ELECTROSTATICS INTERFACE | 83

 POINT SELECTION

Beware that constraining the potential on points usually yields a current

outflow that is mesh dependent.

POINT CHARGE (ON AXIS)

Enter a value or expression to apply a Point charge QP (SI unit: C) to points on an axis.
This source represents an electric displacement field flowing out of the point. The
default is 0 C.

Point Charge and Line Charge (Out-of-Plane)

Change Cross Section

This node is available with 1D components. This setting overrides the global
Cross-Section Area setting made in any physics interface that uses this feature. For 2D
components, see Change Thickness (Out-of-Plane).

Use the Change Cross Section node to set the cross-section area for specific geometric
entities.

CHANGE CROSS SECTION

Enter a value or expression for the Cross-section area A. The default value of 1 unit
length is typically not representative for a thin domain. Instead it describes a unit
thickness that makes the 1D equation identical to the equation used for 3D
components.

Change Thickness (Out-of-Plane)

This node is available for 2D components. This setting overrides the global Thickness
setting made in any physics interface that uses this node. For 1D components, see
Change Cross Section.

Use the Change Thickness (Out-of-Plane) node to set the out-of-plane thickness for
specific geometric entities.

84 | CHAPTER 3: AC/DC INTERFACES

CHANGE THICKNESS (OUT-OF-PLANE)
Enter a value or expression for the Out-of-plane thickness d (SI unit: m). The default
value is, in most cases, 1 unit length, which is typically not representative for a thin
domain. Instead it describes a unit thickness that makes the 2D equation identical to
the equation used for 3D components.

Charge Conservation, Piezoelectric

This feature is available with the Piezoelectricity interface, which requires

the Acoustics Module, MEMS Module, or the Structural Mechanics
Module. See the individual documentation for information.

The Charge Conservation, Piezoelectric node is normally used together with a

Piezoelectric Effect multiphysics coupling node and a corresponding Piezoelectric
Material node in the Solid Mechanics interface. The node is added by default to the
Electrostatics interface when adding a Piezoelectricity interface. It is also available from
the context menu (right-click the Electrostatics interface parent node) or from the
Physics toolbar.

When the Charge Conservation, Piezoelectric node is added to the

electrostatics interface in the absence of an active Piezoelectric Effect
multiphysics coupling node, the material behaves similarly to a Charge
Conservation node, with electric properties corresponding to the relative
permittivity entered (see below). The piezoelectric effect is not included
in the corresponding equation system.

ELECTRIC DISPLACEMENT
If the node is used together with an active Piezoelectric Effect multiphysics coupling
node, then these settings are locked. Note that if they are unlocked, then the material
behaves like a dielectric and not a piezoelectric. In this case, the default is to take the
Relative permittivity rS (dimensionless) values From material. For User defined, select
Isotropic, Diagonal, Symmetric, or Full and enter values or expressions in the field or
matrix.

THE ELECTROSTATICS INTERFACE | 85

 The Electric Currents Interface
The Electric Currents (ec) interface ( ), under the AC/DC>Electric Fields and Currents
branch when adding a physics interface, is used to compute electric field, current, and
potential distributions in conducting media under conditions where inductive effects
are negligible; that is, when the skin depth is much larger than the studied device.

Depending on the licensed products, stationary, frequency-domain, small-signal

analysis, and time-domain modeling are supported in all space dimensions. In the time
and frequency domains, capacitive effects are also accounted for.

The physics interface solves a current conservation equation based on Ohm’s law using
the scalar electric potential as the dependent variable.

Current Conservation is the main node, which adds the equation for the electric
potential and provides a Settings window for defining the electrical conductivity as well
as the constitutive relation for the electric displacement field and its associated material
properties, such as the relative permittivity.

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

Physics-Controlled Mesh
The physics-controlled mesh is controlled from the Mesh node’s Settings window (if the
Sequence type is Physics-controlled mesh). There, in the table in the Physics-Controlled
Mesh section, find the physics interface in the Contributor column and select or clear
the check box in the Use column on the same table row for enabling (the default) or
disabling contributions from the physics interface to the physics-controlled mesh.

Information from the physics, such as the presence of an infinite elements domain or
periodic condition, will be used to automatically set up an appropriate meshing
sequence.

In the COMSOL Multiphysics Reference Manual see the

Physics-Controlled Mesh section for more information about how to
define the physics-controlled mesh.

86 | CHAPTER 3: AC/DC INTERFACES

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 ec.

CROSS-SECTION AREA (1D)

Enter a default value for the Cross-section area A (SI unit: m2). The default value of 1
is typically not representative for a thin domain. Instead it describes a unit thickness
that makes the 1D equation identical to the equation used for 3D components. See
also (described for the Electrostatics interface).

THICKNESS (2D)
Enter a default value for the Out-of-plane thickness d (SI unit: m) (see ). The default
value of 1 m is typically not representative for a thin dielectric medium, for example.
Instead it describes a unit thickness that makes the 2D equation identical to the
equation used for 3D components. See also (described for the Electrostatics
interface).

DEPENDENT VARIABLES
The dependent variable is the Electric potential V. You can change its name, which
changes both the field name and the variable name. If the new name coincides with the
name of another electric potential field in the model, the physics interfaces share
degrees of freedom. The new name must not coincide with the name of a field of
another type or with a component name belonging to some other field.

DISCRETIZATION
Select the shape order for the Electric potential dependent variable — Linear, Quadratic
(the default), Cubic, Quartic, or Quintic. For more information about the Discretization
section, see Settings for the Discretization Sections in the COMSOL Multiphysics
Reference Manual.

• Domain, Boundary, Edge, Point, and Pair Nodes for the Electric
Currents Interface

THE ELECTRIC CURRENTS INTERFACE | 87

 Pacemaker Electrode: Application Library path COMSOL_Multiphysics/
Electromagnetics/pacemaker_electrode

Domain, Boundary, Edge, Point, and Pair Nodes for the Electric
Currents Interface
The Electric Currents interface has these domain, boundary, edge, point, and pair
nodes available from the Physics ribbon toolbar (Windows users) or Physics context
menu (Mac or Linux users). You can also 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.

ABOUT THE BOUNDARY CONDITIONS

The exterior and interior boundary conditions listed in Table 3-1 are available. The
relevant physics interface condition at interfaces between different media and interior
boundaries is continuity; that is,

n2   J1 – J2  = 0

which is the natural boundary condition.

88 | CHAPTER 3: AC/DC INTERFACES

AVAILABLE NODES
These nodes are available for this physics interface, listed in alphabetical order. Also see
Table 3-1 for a list of interior and exterior boundary conditions, including edge, point,
and pair availability.

• Boundary Current Source • Initial Values

• Contact Impedance • Line Current Source
• Current Conservation • Line Current Source (on Axis)
• Current Source • Normal Current Density
• Distributed Impedance • Piezoresistive Material1
• Electric Insulation • Point Current Source
• Sector Symmetry

1This feature is available with the Piezoresistivity, Domain Currents interface, which

requires the MEMS Module.

These nodes are described for the Electrostatics interface:

• Change Cross Section • Ground

• Change Thickness (Out-of-Plane) • Periodic Condition
• Electric Potential

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.

For axisymmetric components, COMSOL Multiphysics takes the axial

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

THE ELECTRIC CURRENTS INTERFACE | 89

 Table 3-1 lists the interior and exterior boundary conditions available with this physics
interface. It also includes edge, point, and pair availability.
TABLE 3-2: INTERIOR AND EXTERIOR BOUNDARY CONDITIONS (INCLUDING EDGE, POINT, AND PAIR
AVAILABILITY) FOR THE ELECTRIC CURRENTS INTERFACE

NODE INTERIOR EXTERIOR ALSO AVAILABLE FOR

Boundary Current Source x pairs

Contact Impedance x pairs
Distributed Impedance x x not applicable
Electric Insulation x x pairs
Electric Potential x x edges, points, and pairs
Ground x x edges, points, and pairs
Normal Current Density x not applicable
Periodic Condition x not applicable

Current Conservation
The Current Conservation node adds the continuity equation for the electrical potential
and provides an interface for defining the electric conductivity as well as the
constitutive relation and the relative permittivity for the displacement current.

MATERIAL TYPE
The Material type setting decides how materials behave and how material properties are
interpreted when the mesh is deformed. Select Solid for materials whose properties
change as functions of material strain, material orientation, and other variables
evaluated in a material reference configuration (material frame). Select Non-solid for
materials whose properties are defined only as functions of the current local state at
each point in the spatial frame, and for which no unique material reference
configuration can be defined. Select From material to pick up the corresponding setting
from the domain material on each domain.

CONSTITUTIVE RELATION JC-E

By default, the Electrical conductivity (SI unit: S/m) for the media is defined From
material. Or select User defined or Linearized resistivity.

User Defined
For User defined select Isotropic, Diagonal, Symmetric, or Full depending on the
characteristics of the electrical conductivity, and then enter values or expressions for the
electrical conductivity in the field or matrix. The default is 0 S/m. If type of

90 | CHAPTER 3: AC/DC INTERFACES

temperature dependence is used other than a linear temperature relation, enter any
expression for the conductivity as a function of temperature.

Linearized Resistivity
Select Linearized resistivity for a temperature-dependent conductivity (this occurs in,
for example, Joule heating, and is also called resistive heating). The equation
describing the conductivity:

1
 = ---------------------------------------------------
 0  1 +   T – T ref  

where 0 is the resistivity at the reference temperature Tref, and  is the temperature
coefficient of resistance, which describes how the resistivity varies with temperature.

The default Reference resistivity 0 (SI unit: m), Reference temperature Tref
(SI unit: K), and Resistivity temperature coefficient  (SI unit: 1/K) are taken From
material, which means that the values are taken from the domain (or boundary)
material. T is the current temperature, which can be a value that is specified as a model
input or the temperature from a heat transfer interface. The definition of the
temperature field is in the Model Inputs section.

To specify other values for any of these properties, select User defined from the list and
then enter a value or expression for each. The default values are:

• 1 m for the Reference resistivity

• 273.15 K for the Reference temperature, and
• 0 1/K for the Resistivity temperature coefficient

CONSTITUTIVE RELATION D-E

Select a Dielectric model to describe the macroscopic properties of the medium
(relating the electric displacement D with the electric field E) and the applicable
material properties, such as the relative permittivity. For a description of the
constitutive relations Relative permittivity, Polarization, and Remanent electric
displacement, see Electric Field as described for the node for the Electrostatics interface.
The constitutive relations specific to Electric Currents are:

• Dielectric losses: uses the constitutive relation D  0'  "E. Specify that the
Relative permittivity (real part) ' (dimensionless) and the Relative permittivity
(imaginary part) " (dimensionless) must be taken From material or be User defined.
For User defined, select Isotropic, Diagonal, Symmetric, or Full and enter values or
expressions in the field or matrix. The default is 1.

THE ELECTRIC CURRENTS INTERFACE | 91

 • Loss tangent, loss angle: uses the constitutive relation D  0'jtanE. Specify the
Relative permittivity (real part) ' (dimensionless) and Loss angle  (SI unit: rad).
• Loss tangent, dissipation factor: uses the constitutive relation D  0'jtanE.
Specify the Relative permittivity (real part) ' (dimensionless) and the Dissipation
factor tan (dimensionless).

Initial Values
The Initial Values node adds an initial value for the electric potential that can serve as
an initial condition for a transient simulation or as an initial guess for a nonlinear solver.
If more than one set of initial values is required, from the Physics toolbar, add other
nodes that implement, for example, boundary conditions and current sources. Add
more Initial Values nodes from the Physics toolbar.

INITIAL VALUES
Enter a value or expression for the initial value of the Electric potential V (SI unit: V).
The default value is 0 V.

External Current Density

The External Current Density node adds an externally generated current density Je,
which appears in Ohm’s law

J = E + J e

and in the equation that the physics interface defines.

The external current density does not contribute to the losses (due to Joule heating),
since there is no electric field associated with it. To include the contribution to the
losses from the external current density, select the Add contribution of the external
current density to the losses check box. Then select an option from the External losses
list — From domain conductivity (the default) or User defined. If From domain
conductivity is selected, the heat source is computed using the conductivity specified in
the material model feature (such as Current Conservation) that is applied in the domain.
For User defined, enter a value for Qe (SI unit: W/m3) to specify a user-defined heat
source.

Add a contribution as a Harmonic Perturbation by right-clicking the parent node or

clicking Harmonic Perturbation on the Physics toolbar. For more information see
Harmonic Perturbation — Exclusive and Contributing Nodes.

92 | CHAPTER 3: AC/DC INTERFACES

EXTERNAL CURRENT DENSITY
Based on space dimension, enter the coordinates (x, y, and z for 3D components, for
example) of the External current density Je (SI unit: A/m2). The defaults are 0 A/m2.

Current Source
The Current Source node adds a distributed current source Qj in the equation that the
physics interface defines. Use this node with caution as it can violate the current
conservation law that is inherent in Maxwell-Ampère’s law.

Add a contribution as a Harmonic Perturbation by right-clicking the parent node or

clicking Harmonic Perturbation on the Physics toolbar. For more information see
Harmonic Perturbation — Exclusive and Contributing Nodes.

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

Electric Insulation
The Electric Insulation node, which is the default boundary condition, adds electric
insulation as the boundary condition:

nJ = 0

This boundary condition means that no electric current flows into the boundary. At
interior boundaries, it means that no current can flow through the boundary and that
the electric potential is discontinuous across the boundary. It is also applicable at
symmetric boundaries where the potential is known to be symmetric with respect to
the boundary.

Electric insulation as the default boundary condition is not applicable to interior

boundaries. To add electric insulation to an interior boundary, add an Electric
Insulation node in addition to the one that represents the default boundary condition.

Boundary Current Source

The Boundary Current Source node adds a current source Qj on the boundary.

n   J1 – J2  = Q j

THE ELECTRIC CURRENTS INTERFACE | 93

 It is applicable to interior boundaries that represent either a source or a sink of current.
Add a contribution as a Harmonic Perturbation by right-clicking the parent node or
click Harmonic Perturbation on the Physics toolbar. For more information see
Harmonic Perturbation — Exclusive and Contributing Nodes.

BOUNDARY CURRENT SOURCE

Enter a value or expression for the Boundary current source Qj (SI unit: A/m2). The
default is 0 A/m2.

Normal Current Density

The Normal Current Density node is applicable to exterior boundaries that represent
either a source or a sink of current. It provides a condition for specifying the normal
current density as an inward or outward current flow:

–n  J = Jn

Or alternatively, as a current density J0:

n  J = n  J0

The normal current density is positive when the current flows inward in the domain.
Add a contribution as a Harmonic Perturbation by right-clicking the parent node or
clicking Harmonic Perturbation on the Physics toolbar. For more information see
Harmonic Perturbation — Exclusive and Contributing Nodes.

NORMAL CURRENT DENSITY

Select a Type — Inward current density (the default) or Current density.

• For Inward current density enter a value or expression for the Normal current density
Jn (SI unit: A/m2). Use a positive value for an inward current flow or a negative
value for an outward current flow. The default is 0 A/m2.
• For Current density enter values or expressions for the components of the Current
density J0 (SI unit: A/m2). The defaults are 0 A/m2.

Distributed Impedance
The Distributed Impedance node adds a distributed impedance boundary condition to
a model.

94 | CHAPTER 3: AC/DC INTERFACES

The Harmonic Perturbation subnode (it is of the exclusive type) is available from the
context menu (right-click the parent node) or on the Physics toolbar, click the
Attributes menu and select Harmonic Perturbation. For more information see Harmonic
Perturbation — Exclusive and Contributing Nodes.

Use this boundary condition to model a thin sheet of a resistive material connected to
a reference potential Vref.

The layer impedance can be specified either with the bulk material conductivity s, the
relative permittivity r and layer thickness ds, or directly with the surface resistance s
and capacitance Cs. Assuming DC currents, the equation is:

s
n   J 1 – J 2  = -----  V – V ref 
ds
1
n   J 1 – J 2  = -----  V – V ref 
s

DISTRIBUTED IMPEDANCE
Enter the reference potential Vref (SI unit: V). The default is 0 V.

Select a potentially complex-valued Layer specification — Thin layer (the default) or

Surface impedance.

• For Thin layer, enter values or expressions for the:

- Surface thickness ds (SI unit: m). The default is 5·103 m (5 mm).
- Electrical conductivity  (SI unit: S/m) and Relative permittivity r
(dimensionless). The defaults take values From material. For User defined, enter
different values or expressions. The default electrical conductivity is 1·102 S/m
and the default relative permittivity is 1.
• For Surface impedance, enter values or expressions for the Surface resistance s
(SI unit: ·m2) and the Surface capacitance Cs (SI unit: Fm2). The default surface
impedance is 1·108 ·m2 and the default surface capacitance is 0 Fm2.

Contact Impedance
Use the Contact Impedance node on interior boundaries to model a thin layer of
resistive material. It can also be added as a pair using a Pair Contact Impedance node.
The feature allows specifying the contact impedance either by entering the properties
of the material together with the layer thickness, or by entering the impedance
properties of the thin layer directly.

THE ELECTRIC CURRENTS INTERFACE | 95

 The feature applies the following conditions that relate the normal electric current
density with the jump in the electric potential:


n  J 1 = ------  V 1 – V 2 
ds

n  J 2 = ------  V 2 – V 1 
ds
1
n  J 1 = -----  V 1 – V 2 
s
1
n  J 2 = -----  V 2 – V 1 
s

The first two equations refer to a layer impedance specified using the bulk material
conductivity s and the layer thickness ds, while the last two equations refer to the case
in which the surface resistance s is specified. The indices 1 and 2 refer to the two sides
of the boundary. These parameters work the same as with Distributed Impedance.

CONTACT IMPEDANCE
Select a potentially complex-valued Layer specification — Thin layer (the default) or
Surface impedance.

• For Thin layer, enter values or expressions for the:

- Surface thickness ds (SI unit: m). The default is 5·103 m (5 mm).
- Electrical conductivity  (SI unit: S/m) and Relative permittivity r
(dimensionless). The defaults take values From material. For User defined, enter
different values or expressions. The default electrical conductivity is 1·102 S/m
and the default relative permittivity is 1.
• For Surface impedance, enter values or expressions for the Surface resistance s (SI
unit: ·m2) and the Surface capacitance Cs (SI unit: Fm2). The default surface
impedance is 1·108 ·m2 and the default surface capacitance is 0 Fm2.

Thin-Film Resistance: Application Library path COMSOL_Multiphysics/

Electromagnetics/thin_film_resistance

Sector Symmetry
Select Sector Symmetry at interfaces between rotating objects where sector symmetry
is used. It is only available for pairs. A default subnode is added. Right-click to select

96 | CHAPTER 3: AC/DC INTERFACES

additional features from the Fallback Features submenu. In 2D, this feature assumes
rotation around the origin.

This feature is always used in conjunction with a on adjacent radial sector

boundaries. Note that the same periodic condition feature cannot be used
on both sides of where the sector symmetry boundaries connect with the
periodic boundaries. At least two periodic condition features are required
for the model to compute correctly.

PAIR SELECTION
When using nonconforming meshes on the source and destination of a pair, for
numerical stability, a finer mesh should be applied on the destination side for any pair
with a condition that imposes a coupling or a constraint across the pair. The sector
symmetry feature falls into this category.

SECTOR SETTINGS
Enter the Number of sectors (<50) nsect. The default is 2.

Select a Type of periodicity — Continuity (the default) or Antiperiodicity.

Based on space dimension, enter values or expressions in the table for the Axis of
rotation arot.

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

Line Current Source

The Line Current Source node adds a line source to edges in 3D components and to
points in 2D and 2D axisymmetric components. The line source represents electric
current per unit length.

EDGE OR POINT SELECTION

Beware that constraining the potential on edges or points usually yields a

current outflow that is mesh dependent.

THE ELECTRIC CURRENTS INTERFACE | 97

 LINE CURRENT SOURCE
Enter a value or expression to apply a Line current source Qj (SI unit: A/m). This
source represents electric current per unit length. The default is 0 A/m.

Line Current Source (on Axis) for 2D axisymmetric components.

Line Current Source (on Axis)

The Line Current Source (on Axis) node adds a line source to boundaries in 2D
axisymmetric components. The line source represents electric current per unit length.

LINE CURRENT SOURCE (ON AXIS)

Enter a value or expression to apply a Line current source Qj (SI unit: A/m) to
boundaries. This source represents electric current per unit length.

Line Current Source

Point Current Source

The Point Current Source node adds a point source and represents an electric current
flowing out of the point. Add point sources to 3D components from the Points menu.
Add a contribution as a Harmonic Perturbation by right-clicking the parent node or
clicking Harmonic Perturbation on the Physics toolbar. For more information see
Harmonic Perturbation — Exclusive and Contributing Nodes.

POINT SELECTION

Beware that constraining the potential on points usually yields a current

outflow that is mesh dependent.

98 | CHAPTER 3: AC/DC INTERFACES

POINT CURRENT SOURCE
Enter a value or expression to apply a Point current source Qj (SI unit: A) to points.
This source represents an electric current flowing out of the point.

• Line Current Source for 2D components

• Point Current Source (on Axis) for 2D axisymmetric components

Point Current Source (on Axis)

The Point Current Source (on Axis) node adds a point source and represents an electric
current flowing out of the point in 2D axisymmetric components.

POINT SELECTION

Beware that constraining the potential on points usually yields a current

outflow that is mesh dependent.

POINT CURRENT SOURCE

Enter a value or expression to apply a Point current source Qj (SI unit: A) to points.
This source represents an electric current flowing out of the point.

• Point Current Source for 3D components

• Line Current Source for 2D components

Piezoresistive Material
The Piezoresistive Material is normally used together with a Piezoresistive Effect, Domain
Currents multiphysics coupling node. The node is added by default to the Electric
Currents interface when adding a Piezoresistivity, Domain Currents predefined

THE ELECTRIC CURRENTS INTERFACE | 99

 multiphysics coupling interface. It is also available from the context menu (right-click
the Electric Currents interface parent node) or from the Physics toolbar.

When the Piezoresistive Material node is added to the Electric Currents

interface in the absence of an active Piezoelectric Effect, Domain Currents
multiphysics coupling node, the material behaves similarly to a Current
Conservation node, with electric properties corresponding to the relative
permittivity and electrical conductivity entered. The piezoresistive effect
is not included in the corresponding equation system.

PIEZORESISTIVE MATERIAL PROPERTY

This node should be used together with an active Piezoresistive Effect, Domain Currents
multiphysics coupling node. Select a Constitutive model — Piezoresistance form or
Elastoresistance form. For each of the following, the default uses values From material.
For User defined enter other values in the matrix or field.

• Specify a Electrical conductivity, zero stress (SI unit: S/m). This typically comes from
the material added under the Materials node.
• For Piezoresistance form, select a Piezoresistance coupling matrix l (SI unit: m4/
(sA2); note that this is equivalent to m/Pa).
• For a Elastoresistance form, select an Elastoresistance coupling matrix Ml
(SI unit: m).

100 | CHAPTER 3: AC/DC INTERFACES

T he o r y f o r th e E l ec t rost at i cs
Interface
is available for 3D, 2D in-plane, and 2D axisymmetric components. Applications with
electrostatic equations include high-voltage apparatus, electronic devices, and
capacitors. The term “statics” is not to be interpreted literally — it is the observation
time, or time scale at which the applied excitation changes, that is short compared to
the charge relaxation time; also, the electromagnetic wavelength and skin depth are
very large compared to the size of the domain of interest.

If you do not know whether to use the Electric Currents or the Electrostatics interface,
which both solve for the scalar electric potential V, consider using an explicit charge
transport model. See Charge Relaxation Theory.

Charge Relaxation Theory

COMSOL Multiphysics includes physics interfaces for the modeling of static electric
fields and currents. Deciding what specific physics interface and study type to select for
a particular modeling situation requires a basic understanding of the charge dynamics
in conductors.

The different physics interfaces involving only the scalar electric potential can be
interpreted in terms of the charge relaxation process. The fundamental equations
involved are Ohm’s law for the conduction current density

J c = E

the equation of continuity

-----
-
+   Jc = 0
t

and Gauss’ law

   E  = 

By combining these, one can deduce the following differential equation for the space
charge density in a homogeneous medium

THEORY FOR THE ELECTROSTATICS INTERFACE | 101

 -----
- 
+ ---  = 0
t 

This equation has the solution

–t  
  t  = 0 e

where


 = ---


is called the charge relaxation time. For a good conductor like copper,  is of the order
of 1019 s, whereas for a good insulator like silica glass, it is of the order of 103 s. For
a pure insulator, it becomes infinite.

When modeling real-world devices, there is not only the intrinsic time scale of the
charge relaxation time but also an external time scale t at which a device is energized
or the observation time. It is the relation between the external time scale and the
charge relaxation time that determines what physics interface and study type to use.
The results are summarized in Table 3-3 below,
TABLE 3-3: SUITABLE PHYSICS INTERFACE AND STUDY TYPE FOR DIFFERENT TIME-SCALE REGIMES.

CASE PHYSICS INTERFACE STUDY TYPE

>>t Electrostatics Stationary

<<t Electric Currents Stationary
~ t Electric Currents Time Dependent orFrequency Domain

FIRST CASE:  >> T

If the external time scale is short compared to the charge relaxation time, the charges
do not have time to redistribute to any significant degree. Thus the charge distribution
can be considered as a given model input. The best approach is to solve the
Electrostatics formulation using the electric potential V.

By combining the definition of the potential with Gauss’ law, you can derive the
classical Poisson’s equation. Under static conditions, the electric potential V is defined
by the equivalence E  V. Using this together with the constitutive relation D0E
P between D and E, you can rewrite Gauss’ law as a variant of Poisson’s equation

–     0 V – P  = 

102 | CHAPTER 3: AC/DC INTERFACES

This equation is used in the Electrostatics interface. It is worth noting that Gauss’ law
does not require the charge distribution to be static. Thus, provided dynamics are slow
enough that induced electric fields can be neglected and hence a scalar electric
potential is justified, the formulation can be used also in the Time Dependent study
type. That typically involves either prescribing the charge dynamics or coupling a
separate formulation for this.

Such separate charge transport formulations can be found in the Plasma

Module, the Semiconductor Module, and the Chemical Reaction
Engineering Module.

SECOND CASE:  <<T

If the external time scale is long compared to the charge relaxation time, the stationary
solution to the equation of continuity has been reached. In a stationary coordinate
system, a slightly more general form of Ohm’s law than above states that

J c = E + J e

where Je is an externally generated current density. The static form of the equation of
continuity then reads

  J c = –     V – J e  = 0

To handle current sources, the equation can be generalized to

–     V – J e  = Q j

This equation is used in the static study type for the Electric Currents interface.

Electrostatics Equations
Under static conditions, the electric potential, V, is defined by the relationship:

E = – V

Combining this equation with the constitutive relationship D  0E  P between the
electric displacement D and the electric field E, it is possible to represent Gauss’ law
as the following equation:

–     0 V – P  = 

THEORY FOR THE ELECTROSTATICS INTERFACE | 103

 In this equation, the physical constant, 0 (SI unit: F/m) is the permittivity of vacuum,
P (SI unit: C/m2) is the electric polarization vector, and  (SI unit: C/m3) is a space
charge density. This equation describes the electrostatic field in dielectric materials.

For in-plane 2D modeling, the Electrostatics interface assumes a symmetry where the
electric potential varies only in the x and y directions and is constant in the z direction.
This implies that the electric field, E, is tangential to the xy-plane. With this symmetry,
the same equation is solved as in the 3D case. The physics interface solves the following
equation where d is the thickness in the z direction:

–   d   0 V – P  = 

The axisymmetric version of the physics interface considers the situation where the
fields and geometry are axially symmetric. In this case, the electric potential is constant
in the  direction, which implies that the electric field is tangential to the rz-plane.

The Electrostatics Interface in Time Dependent or Frequency Domain

Studies
can also be solved in a dynamic study (Time Dependent or Frequency Domain). The
equation system solved, however, is typically always the one presented in the previous
section for the stationary case, in which no transient electromagnetic effects are taken
into account. The difference is that the sources of the problem (charge densities,
electric potential) are assumed to be time-varying (in a Time Dependent study) or
time-harmonic (in a Frequency Domain study).

The support for dynamic studies simplifies the coupling of the Electrostatics interface
with other physics interfaces. Using the physics interface in a dynamic study is a valid
approximation only if the time-scale (or the frequency) of the study is so slow that
transient electromagnetic effects can be neglected; for example, in acoustic or
structural problems.

The Electrostatics interface also supports the small-signal analysis study sequence,
which can be used when a time-harmonic perturbation is superposed on a static bias
charge or voltage.

104 | CHAPTER 3: AC/DC INTERFACES

Theory for the Electric Currents
Interface
solves a current conservation problem for the scalar electric potential V and is available
for 3D, 2D in-plane, and 2D axisymmetric components. Electrolysis and the
computation of resistances of grounding plates are examples that involve conductive
media with electrical conductivities and electric currents. If you are uncertain of
whether to use the Electric Currents or the Electrostatics interface, which both solve
for the scalar electric potential V, refer to the section on .

Electric Currents Equations in Steady State

When handling stationary electric currents in conductive media you must consider the
stationary equation of continuity. In a stationary coordinate system, the point form of
Ohm’s law states that:

J = E + J e

where  is the electrical conductivity (SI unit: S/m), and Je is an externally generated
current density (SI unit: A/m2). The static form of the equation of continuity then
states:

  J = –     V – J e  = 0

To handle current sources, you can generalize the equation to:

–     V – J e  = Q j

In planar 2D the Electric Currents interface assumes that the model has a symmetry
where the electric potential varies only in the x and y directions and is constant in the
z direction. This implies that the electric field, E, is tangential to the xy-plane. The
Electric Currents interface then solves the following equation, where d is the thickness
in the z direction:

–   d   V – J e  = dQ j (3-1)

In 2D axisymmetry, the Electric Currents interface considers the situation where the
fields and geometry are axially symmetric. In this case, the electric potential is constant
in the  direction, which implies that the electric field is tangential to the rz-plane.

THEORY FOR THE ELECTRIC CURRENTS INTERFACE | 105

106 | CHAPTER 3: AC/DC INTERFACES
 4

Electrochemistry Interfaces

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

In this chapter:

• The Primary and Secondary Current Distribution Interfaces

• The Tertiary Current Distribution, Nernst-Planck Interface
• Shared Physics Features in the Current Distribution Interfaces
• The Electrode, Shell Interface
• The Electroanalysis 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

107
 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 both found under the Electrochemistry
branch ( ) when adding a physics interface.

Primary Current Distribution Interface

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

108 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

Secondary Current Distribution Interface

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

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

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

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

• Introduction to Electrochemistry Modeling

SETTINGS
The Label is the default physics interface name.

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

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

DOMAIN SELECTION

Domains that do not conduct current should be omitted from the

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

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 109

 OUT-OF-PLANE THICKNESS

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

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

CROSS-SECTIONAL AREA

For 1D components, enter a Cross-sectional area Ac (SI unit: m2) to define

a parameter for the area of the geometry perpendicular to the 1D
component. The value of this parameter is used, among other things, to
automatically calculate the total current from the current density vector.
The analogy is valid for other fluxes. The default is 1 m2.

CURRENT DISTRIBUTION TYPE

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

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

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

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.

110 | CHAPTER 4: 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
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

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

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

The Electrolyte conductivity, l (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.

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 111

 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.

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

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.

112 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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).

FILM RESISTANCE
See the Electrode Surface node.

• Domain Equations for Primary and Secondary Current Distributions

• Porous Electrode Theory

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

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.

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 113

 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.

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

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

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

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

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

114 | CHAPTER 4: 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.

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.

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.

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 115

 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.

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.

116 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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.

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 117

 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

118 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

Introduction to Electrochemistry Modeling

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

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

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

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

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

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

ELECTROLYTE CHARGE CONSERVATION

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

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 119

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

120 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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,

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 121

 which is not selected by default. Any settings unique to this physics interface are listed
below.

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

In the COMSOL Multiphysics Reference Manual see Table 2-4 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.

122 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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.

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 123

 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

124 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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 l. (l 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.

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 125

 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.

126 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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.

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 127

 Shared Physics Features in the
Current Distribution Interfaces
Domain, Boundary, Pair, Edge, and Point Nodes for the
Electrochemistry Interfaces
Electrochemistry Interfaces interfaces have these domain, boundary, edge, point, and
pair nodes, listed in alphabetical order, available from the Physics ribbon toolbar
(Windows users), Physics context menu (Mac or Linux users), or right-click to access
the context menu (all users).

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

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

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

128 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

• Double Layer Capacitance • Electrolyte Current Source
• Circuit Terminal • Electrolyte Potential
• Electric Ground • External Short
• Electric Potential • Harmonic Perturbation
• Electric Reference Potential • Highly Conductive Porous
• Electrode Electrode

• Electrode Current • Initial Values for

Dissolving-Depositing Species
• Electrode Current Density
• Insulation
• Electrode Current Source
• Internal Electrode Surface
• Electrode-Electrolyte Boundary
Interface • Line Mass Source1

• Electrode Potential • Non-Faradaic Reactions

• Electrode Reaction • Point Mass Source1

• Electrode Surface • Porous Electrode Reaction

• Electrolyte Current Density • Porous Matrix Double Layer

Capacitance
• Reference Electrode
• Symmetry
• Thin Electrode Layer
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

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 129

 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 s (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 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 = –  s  s

and s denotes the electrode’s conductivity and  s the electric potential.

130 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 131

 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

132 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

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.

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

Use The Surface Reactions Interface to model surface diffusion.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 133

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

Specify either a Surface resistance Rfilm (SI unit: ·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.

134 | CHAPTER 4: 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 4-1: 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 | 135

 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.

136 | CHAPTER 4: 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 | 137

 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

138 | CHAPTER 4: 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, a (dimensionless), and Cathodic transfer coefficient, c

(dimensionless), parameters will impact how much iloc will change upon changes in the
overpotential. In order to ensure thermodynamic consistency, c 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, c 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, a (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, c (SI unit: V), describes the required decrease in
overpotential to result in a tenfold increase in the current density magnitude. c
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 | 139

 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:

 ox Sox + ne  red Sred

-
 (4-1)
ox red

140 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Set i as positive (red) for the reduced species and negative (ox) 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 | 141

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

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

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

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

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

Internal Electrode Surface

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

Electrode domain
s
Electrolyte domain
l

Internal Electrode Surface

142 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

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,  l, to be equal to the Boundary
electrolyte potential,  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.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 143

 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.

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

144 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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.

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

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

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

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

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

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

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 145

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

 s =  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.

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.

146 | CHAPTER 4: 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.

• 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

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

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 147

 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  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).

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

 s =  s here

 s here –  s there
 s here :   n  Is dd = – ---------------------------------------
R
-
d

where  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  s there .

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

148 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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.

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

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

Electrode Potentials and Reference Electrodes

Electric Reference Potential

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

Electrode Potentials and Reference Electrodes

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 149

 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.

150 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

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

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

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

SETTINGS
The Label is the default physics interface name.

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

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

THICKNESS

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

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

THE ELECTRODE, SHELL INTERFACE | 151

 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.

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.

152 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

These physics nodes are described in this section:

• Boundary Current Source • Electric Potential

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

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

• Electrode Potential
• Electric Reference Potential

For axisymmetric components, COMSOL Multiphysics takes the axial

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

In the COMSOL Multiphysics Reference Manual see Table 2-4 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 (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

THE ELECTRODE, SHELL INTERFACE | 153

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

Theory for the Electrode, Shell Interface

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

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

External Current Density

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

EXTERNAL CURRENT DENSITY

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

Current Source
The Current Source node adds a source term to Equation 4-7. 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.

154 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

T  is = in

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

NORMAL CURRENT DENSITY

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

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

Boundary Current Source

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

i s  n = i s 0

BOUNDARY CURRENT SOURCE

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

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

THE ELECTRODE, SHELL INTERFACE | 155

 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  s =  s 0 .

EDGE OR POINT SELECTION

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

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

ELECTRIC POTENTIAL
Enter the value or expression for the Electric potential  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.

156 | CHAPTER 4: 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 | 157

 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

158 | CHAPTER 4: 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  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),
•  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  l (4-2)

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 l .
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
l = F

the current density in the electrolyte can be written as

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 159

 i l = –  l  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 porous electrode

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

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

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

  ik = Qk

with

i k = –  k  k

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

160 | CHAPTER 4: 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 m, is the following:

 m =  s –  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, m, 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:

 l =  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:

 a F –  c F
i loc,m = i 0  exp  --------------- – exp  ----------------- 
RT RT

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 161

 where iloc,m denotes the local charge transfer current density for reaction m, i0 the
exchange current density, a the anodic transfer coefficient, c 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.

162 | CHAPTER 4: 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 4-2)

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  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 | 163

  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:

 ox Sox + ne  red Sred

-

ox red

is used to define the stoichiometric coefficients, i, with i being positive (red) for
products and negative (ox) 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:

 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

164 | CHAPTER 4: 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:

 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, i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  i m i loc m
v dep tot =  ------
i  nm F
- -------------------------- (4-3)
i m

Where Mi (SI unit: kg/mol) is the molar mass and i (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 | 165

 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  i m i loc m
dt
=  -------------------------
nm F
-
m

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

Mi
s tot =  ------
-c .
 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 A = 1, X = 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

166 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

variable for the potential drop over the film,   s,film, is introduced. The governing
equation is:

 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, m, for all occurring
electrode reactions on the electrode with the film receive an extra potential
contribution due to the film resistance according to:

 m =  s –  s film –  l – E 0 m

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

s 0 + s
R film = ------------------
 film

where s0 is the reference/initial film thickness, s the electrode thickness change, and
film 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

 
-
 i S i + ne  i Si
i: i  0 i: i  0

where i 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,  s –  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, G, as

G
E eq = – --------
nF

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 167

 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 i
  ------------
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  (V), is the following:

 =  s –  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:

 a F –  c F
i loc = i 0  exp  --------------- – exp  ----------------- 
  RT   RT  

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

168 | CHAPTER 4: 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 a  c  n, then the exchange
current density becomes as follows:

c i –a i
---------
- --------------
ai 
 ------------
n ai 
 ------------
n
i 0 = i 0 ref   a i ref   a i ref
i: i  0 i: 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  i
 ------------  a F ref ai  –i –  c F ref 
- exp  --------------------  ------------ exp  ----------------------- 
i loc = i 0 ref 
   a i ref  RT 
- –
  a i ref
-
 RT  
i: i  0 i: i  0

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

 ref =  s –  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 i
i 0 = i 0 ref   ------------
a i ref
-
i

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 169

 where i are generic exponential coefficients. For this case, a and c may be
independently defined. By rearranging the Butler-Volmer expression using ref
similarly to what was done for the mass action law case above, the i coefficients relate
to the anodic, ai, or cathodic, ci, reaction orders according to

a i
 a i =  i + -----------
n

and

c i
 c i =  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

 a F –  c F
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:

 a F –  c F
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   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.

170 | CHAPTER 4: 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 ( << RT/F) and is usually referred to as
the low-field approximation. This approximation gives the following linearized
equation:

  a +  c F
i loc = i 0  ---------------------------- 
 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:

  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 = ----------------------
a F

The cathodic Tafel expression is defined according to:

  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 = – ----------------------
c 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 | 171

 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 
= r = – kc
dt

where 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 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  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 '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.

172 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

The third case is when is a non-integer between 0 and 1. Note now that Jacobian
with respect to c of the rate expression now contains c, 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, i.e., to use


r = – kc c  c lim

–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 .

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

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 173

 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

174 | CHAPTER 4: 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 .

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

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
where iloc,m (A/m2) is the 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.

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 175

 ELECTRODE THEORY
Electron conduction in an 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 = –  s  s

and where s denotes the electrical conductivity and  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 THEORY

The 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,  l bnd, along the
boundary. It then adds one additional equation for the total current, which is an
integral over the boundary:

176 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

  il  n ds = I n l


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 adds one unknown variable, the electric potential,  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


where

i s = –  s  s

and s denotes the electrode conductivity and  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 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 can be defined as its component perpendicular to the boundary according
to:

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 177

 i s  n = i n s

where

i s = –  s  s

and s denotes the electrode conductivity and  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  s, bnd, defined by the condition for the total power on the boundary 
according to:

 s =  s bnd on 

  s bnd – s ground   is  n  dS = P total



where  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.

178 | CHAPTER 4: 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

 fix + F  zi ci = 0

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

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

 i = RT ln a i +  l z i F

where T(K) is the temperature, R (mol/(J K)) the molar gas constant, ai is the species
activity,  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,  (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
 l =  l 1 –  l 2 = – -------- ln  ---------
RT
zi F  c i 2

which may be rearranged to

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 179

 z i F   l 1 –  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

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.

180 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Theory for Electrochemical Heat
Sources
Irreversible voltage losses in an electrochemical cell can occur due to the following
phenomena:

• Charge transport in the electrolyte (Joule heating)

• Charge transport in the solid conductor materials (Joule heating)
• Activation overpotentials in the electrode reactions
• Heat of mixing

In addition, reversible heat sources and sinks can appear due to the entropy changes in
the electrode reactions.

Most Electrochemistry interfaces define and announce heat source variables that for
instance can be used by the General Source and the Boundary Heat source nodes in
the Heat Transfer interfaces.

An alternative way to couple an electrochemical interface to a heat transfer interface is

by the use of the Multiphysics nodes that become available in the model builder tree if
there is both a Heat Transfer interface and an Electrochemistry interface available in
the same component.

The Electrochemical Heating multiphysics node defines a domain heat source in the
heat transfer interface, based on the sum of irreversible (Joule heating and activation
losses) and reversible heat in the electrochemistry interface.

You can also use the heat source variables defined by the electrochemistry interfaces
when setting up manual heat couplings between different components in a model. For
instance if you are using a 1D electrochemical cell model to calculate an average heat
source in a 3D heat transfer model. The names of the heat source variables are xxx.Qh
(domain, Joule heating and porous electrode reactions) and xxx.Qbfc (boundary,
electrode surface reactions), where xxx is the electrochemistry interface identifier.

• Electrochemistry Interfaces
• Multiphysics Coupling Nodes

THEORY FOR ELECTROCHEMICAL HEAT SOURCES | 181

 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   s + i l   l  (4-4)

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

H m G m
Q m =  ------------- –  ------------- –  m tot  i m (4-5)
nm F nm F

where Hm is the enthalpy change of the reaction, and Gm is the Gibbs free energy
of the reaction, Gm, defined as

G m = H m – TS m

where Sm is the net entropy change. Equation 4-5 may now be rearranged into

TS m
Q m =   m tot + ---------------- i m (4-6)
 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 4-5 we have used the total overpotential, m,tot,(including potential

effects from film resistances and similar), defined as

 m tot =  s –  l – E eq m

The equilibrium potential is related to Gm in the following way:

G m
E eq m = – -------------
nm F

182 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

By the relation between the temperature derivative of the equilibrium potential and the
entropy:

E eq m S m
------------------
- = -----------
-
T nm F

the local heat source due to the electrochemical conversion process becomes

E eq m
Q m =   m tot + T ------------------- i m
 T 

Alternatively, by defining the thermoneutral voltage of the reaction as

H m
E therm m = – -------------
nm F

one may also define the heat source as

Q m =   m tot +  E eq m – E therm m  i m

The total heat source due to the electrochemical reactions, QEC, for an electrode
surface is the sum of all individual heat sources of the electrode reactions according to

Q EC =  Qm
m

For a porous electrode joule heating and electrochemical sources are summed up for a
total heat source in the domain according to

Q TOT p =  av m Qm + QJH

m

Heating Due to Heat of Mixing

If the enthalpy varies with the local concentration of the reacting species of the
reaction, there are also heat of mixing sources associated with the concentration
gradients and resulting molecular flux of the reacting species from the bulk to the
surface that have to been to included for a correct thermal balance of the cell. The heat
of mixing effects are typically small (zero for ideal gases) and are generally not included
in the Electrochemistry interfaces.

THEORY FOR ELECTROCHEMICAL HEAT SOURCES | 183

184 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES
Theory for the Electrode, Shell
Interface
defines electrode current conduction on a thin shell on a boundary. The electrolyte
current distribution in the adjacent domain is typically solved for by a separate physics
interface.

In this section:

• Governing Equations
• Coupling to Other Physics Interfaces

Governing Equations
The Electrode, Shell interface solves for the electric potential  s (SI unit: V) on a
boundary, using the following governing equation:

 T   si s  = – i n (4-7)

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 = – T  s  s (4-8)

where s 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

THEORY FOR THE ELECTRODE, SHELL INTERFACE | 185

 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 + s tot (4-9)

where s0 is the initial electrode layer thickness, and stot 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  s

186 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

THEORY FOR ELECTROANALYSIS | 187

 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  l = 0 .

188 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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  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 (4-10)

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 (4-11)
t

The Electroanalysis charge conservation model solves Equation 4-10 and

Equation 4-11 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 (4-12)
t

THEORY FOR ELECTROANALYSIS | 189

 Equation 4-12 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:

 m =  s –  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 (  l = 0 ), this equation

reduces to:

 m =  s – E eq m

The activation overpotential is independent of the properties of the adjacent

electrolyte. It only depends on the applied electrode potential s and the equilibrium
potential of the redox couple, where both are measured against a common reference
potential.

190 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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:

 i m i m
Ni =  -----------------
nm F
- (4-13)
m

where i,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 (4-14)

Equation 4-13 and Equation 4-14 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 Electrode Kinetics Expressions:

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:

THEORY FOR ELECTROANALYSIS | 191

 I total =  itotal ds


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:

 a F –  c F
i loc = k 0 F  c Red exp  --------------- – c Ox exp  -----------------  (4-15)
  RT   RT  

where k0 is the heterogeneous rate constant (SI unit: m/s) and c is the (cathodic)
transfer coefficient (dimensionless). For a one-electron reduction, the anodic and
cathodic transfer coefficients are related as follows  a +  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 4-15 into the Butler-Volmer equation written in terms of an exchange
current density i0 (SI unit: A/m2):

 a F –  c F
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 .

192 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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,  s, CE, and then solve for this potential to fulfill
the following current balance over all electrode surfaces:

 s CE :  i tot dS = 0 (4-16)
electrodes

The counter electrode potential is used in the overpotential, , in the kinetics

expression(s) on the counter electrode.

 m =  s CE – E eq m (4-17)

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

THEORY FOR ELECTROANALYSIS | 193

 Electrode Potentials and Reference
Electrodes
In all the Electrochemistry branch interfaces, the dependent potential variables are  s
(SI unit: V), the electric potential of the electrode phase (the electron conductor, such
as metal), and  l (SI unit: V), the potential of the electrolyte phase (ion conductor).

Typically the kinetics of the electrochemical reactions are defined using the
overpotential,  (SI unit: V), defined as

 =  s –  l – E eq (4-18)

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 4-18 is that it is the potential difference,  s –  l , that

governs the kinetics, not the absolute individual values of  s and  l. A global change
in the reference for both potentials has no impact on the electrode kinetics. As a result
of this, the potentials have to be “boot-strapped” in a model in some way, typically by
making an arbitrary choice of electric ground — for example, on an external boundary
— in order to ensure that there is a unique solution to the problem.

In this section:

• Reference Electrodes
• Boundary Conditions Using Reference Electrode Potentials
• Nodes for Handling Electrode Potentials and Reference Electrodes

Reference Electrodes
In experimental electrochemistry, it is common to use a reference electrodes when
controlling current or voltage with a potentiostat. Potential differences in the system
are recorded with respect to the equilibrium potential of the redox couple at the
reference electrode. A good reference electrode is designed so that no net charge
transfer takes place at its electrode-electrolyte interface. Then the overpotential of the
reference is zero, so:

194 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

  s ref =  l + E eq ref (4-19)

where  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 =  s –  s ref (4-20)

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

 s bnd = E vs ref +  s ref (4-21)

where  s , bnd (SI unit: V) is the applied electric boundary potential on the electrode.

Nodes for Handling Electrode Potentials and Reference Electrodes

The node is a point feature applicable to electrolyte domains (in all the
Electrochemistry interfaces). It defines a global electric reference potential  s , ref (SI
unit: V) according to Equation 4-19. The  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 4-20, is also defined in all electrode domains.

ELECTRODE POTENTIALS AND REFERENCE ELECTRODES | 195

 The node is a point feature applicable to electrode domains (in all the
Electrochemistry interfaces). It defines a global electric reference potential  s , ref (SI
unit: V) equal to the dependent variable  s (SI unit: V) in the point. The  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  s , ref is defined, the variable Evs ref (SI unit: V), according to
Equation 4-20, is also defined in all electrode domains.

The 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 4-21. 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 4-20, is also defined on these
features.

196 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

 5

Fuel Cell and Electrolyzer Interfaces

This chapter describes the physics interfaces found under the

Electrochemistry>Hydrogen Fuel Cells ( ) and >Water Electrolyzers ( )
branches.

In this chapter:

• The Hydrogen Fuel Cell and Water Electrolyzer Interfaces

• Theory for the Hydrogen Fuel Cell and Water Electrolyzer Interfaces

197
 The Hydrogen Fuel Cell and Water
Electrolyzer Interfaces
The Hydrogen Fuel Cell (fc) and Water Electrolyzer (we) physics interfaces are used to
solve for the electrode and electrolyte phase potentials of the different electron and
ion-conducting layers of various types of hydrogen fuel cells, or water electrolyzer cells.
Optionally, gas phase transport and Darcy’s law for convection in porous media and
flow channels may be enabled and also solved for by the interfaces.

The interface supports simulation in 1D, 2D, and 3D as well as for axisymmetric
components in 1D and 2D.

Note that once added to a model, the Hydrogen Fuel Cell (fc) and the Water
Electrolyzer (we) interfaces are identical in terms of functionality, and only differ by
some default parameter values (see below), the default tag and name (fc/we), and the
icon ( / ).

The Electrochemistry>Hydrogen Fuel Cell ( ) and the Electrochemistry>Water

Electrolyzers ( ) branches in the Model wizard, or in the Select physics tab, contain
a number of different entries for adding either a Hydrogen Fuel Cell (fc) or a Water
Electrolyzer (we) physics interface, of different electrolyte types, to a model.

Depending on the selected entry, different species will be included by default in the
electrode gas mixtures, and gas phase diffusion will be enabled by default if there are
more than one species present a mixture. See also the H2 Gas Mixture and O2 Gas
Mixture section below.

The chosen model wizard entry will also have an effect on the default stoichiometry
and kinetics parameter values used when adding electrode reactions to the model. See
the Electrode Reaction Settings below.

SETTINGS AT THE INTERFACE LEVEL (FC/WE)

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.

198 | CHAPTER 5: FUEL CELL AND ELECTROLYZER INTERFACES

The default Name (for the first physics interface in the model) is fc for the Hydrogen
Fuel Cell interface, and we for the Water Electrolyzer interface.

DOMAIN SELECTION
If any part of the model geometry should not partake in the fuel cell/electrolyzer
model, remove that part from the selection list.

H2 GAS MIXTURE AND O2 GAS MIXTURE

These sections specify what the species are present in the Gas Phase domains on the
respective sides of the cell. Apart from hydrogen and oxygen, which are always
assumed to be present on each side, you may here choose to include one or several of
the species H2O, N2, CO2 and CO.

If you expect concentration gradients in the gas diffusion electrodes (GDEs), gas
diffusion layers (GDLs) or the flow channels, you may chose to Include gas phase
diffusion in these sections. Gas phase diffusion can only be enabled if there are more
than one species present in the gas mixture.

Use Darcy’s law for momentum transfer for solving for the gas phase pressure using
Darcy’s Law in gas phase domains. This can be enabled individually for each gas
mixture in these sections. Note however that instead of using the built-in Darcy’s law
of the fc/we interface, you may instead couple the interface to any Fluid Flow
interface, or an analytical expression, by specifying the velocity explicitly in the Gas
Phase nodes, or by using an Reacting Flow, H2/O2 Gas Phase multiphysics coupling
node.

If Use H2O(l) in Reaction Stoichiometry is enabled, this will allow for setting the
stoichiometric coefficient of liquid water in electrode reactions, which in term may be
used for the built-in calculations of equilibrium and thermoneutral potentials. Unit
activity of H2O(l) will be assumed in all expressions.

ELECTRODE REACTION SETTINGS

In this section you can control the default parameter settings that electrode reactions
will get when added to the model, and how the potential of the global hydrogen
reference electrode will be calculated.

The Electrolyte type setting (Proton exchange, Hydroxide exchange, Molten carbonate,
Solid oxide or Generic) will impact the default stoichiometry of electrode reactions and
a built-in hydrogen reference electrode used for the calculation of equilibrium and
thermoneutral potentials of the electrode reactions.

THE HYDROGEN FUEL CELL AND WATER ELECTROLYZER INTERFACES | 199

 For all types except Generic, the Reference hydrogen electrode equilibrium potential,
Eeq,RHE (V), will be calculated using an internal database of reaction enthalpies and
entropies, in combination with the Reference hydrogen electrode temperature, which
should be a global value with no spatial dependency.

The Generic option will add no default stoichiometric coefficients, and for this case the
Eeq,RHE and the Charge of the charge-carrying ion will have to be specified explicitly.

Note that the Entropy of the charge-carrying ion has no impact on the equilibrium
potentials vs Eeq,RHE, but will have an effect the calculation of the thermoneutral
potentials. (See also Calculation of Built-in Equilibrium and Thermoneutral
Potentials)

The following reaction stoichiometry will be used for calculating Eeq,RHE, and as
default for the electrode reactions on the H2 and O2 sides, respectively.

Proton exchange:

+ -
2H + 2e  H 2 (g)

+ -
O 2 (g) + 4H + 4e  2H 2 O(g)

Hydroxide exchange:

- -
2H 2 O(g) + 2e  H 2 (g) + 2OH

- -
O 2 (g) + 2H 2 O(g) + 4e  4OH

Molten carbonate:

- 2-
H 2 O(g) + CO 2 (g) + 2e  H 2 (g) + CO 3

- 2-
O 2 (g) + 2CO 2 (g) + 4e  2CO 3

Solid oxide:

- 2-
H 2 O(g) + 2e  H 2 (g) + O

- 2-
O 2 (g) + 4e  2O

200 | CHAPTER 5: FUEL CELL AND ELECTROLYZER INTERFACES

The Operation mode setting (Fuel cell or Electrolyzer) will impact the default values of
the kinetics settings of added electrode reactions.

REFERENCE PRESSURE LEVEL

This section is available if the Use Darcy’s law for momentum transport checkbox has
been selected. In this section, you specify the Reference pressure level.

ADVANCED SETTINGS
From the Regularization list, select On (default) or Off. When turned On, regularized
mass fractions are selected such that they lie between 0 and 1. The regularized mass
fractions are used in the calculation of composition-dependent material properties,
such as density.

This section is available when the Advanced Physics Options is selected in the Show More
Options dialog box shown when the Show More Options button ( ) is clicked, in
combination with the Include gas phase diffusion checkbox being selected.

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.

This section is available when the Advanced Physics Options is selected in the Show More
Options dialog box shown when the Show More Options button ( ) is clicked.

OVERVIEW OF THE DOMAIN NODES IN THE HYDROGEN FUEL CELL AND

WATER ELECTROLYZER INTERFACES
The following phase nodes are added as default nodes:

• Electrolyte Phase
• Electronic Conducting Phase
• Gas Phase (H2 and O2)

These default phase nodes define the physics in the different phases of the cell, and
contain settings for, for instance, electrolyte conductivity and gas diffusion coefficients.

THE HYDROGEN FUEL CELL AND WATER ELECTROLYZER INTERFACES | 201

 Initial Values for the dependent variables defined by the phase nodes are available as
subnodes. Boundary conditions for, for instance, potential, current densities, inflow
gas compositions etc, are added as subnodes to the above phase nodes.

The default phase nodes have their selections locked to all domains, but may have their
selections overridden by the following nodes, which may be added by the user:

• Membrane
• Current Collector
• Gas Diffusion Layer (H2 or O2)
• Gas Diffusion Electrode (H2 or O2)
• Flow Channel (H2 or O2)

These nodes define properties that do not pertain to the pure electrolyte or gas phases
such as porosities, permeabilities, and electronic conductivities. Electrode reactions are
added as sub-nodes to the gas diffusion electrode nodes.

Electrolyte Phase
The Electrolyte Phase node defines the governing domain equations for the electrolyte
phase.

Note that node is added by default, and that you cannot alter the selection of the node
by settings on the node itself. The node will be active on domains selected by
Membrane or Gas Diffusion Electrode nodes.

ELECTROLYTE CHARGE TRANSPORT

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

See also Electrolyte Phase Theory.

Electronic Conducting Phase

The Electronic Conducting Phase node defines the governing equations for the
electronic conducting (electrode) phase.

Note that node is added by default, and that you cannot alter the selection of the node
by settings on the node itself. The node will be active on domains selected by Current
Collector, Gas Diffusion Layer or Gas Diffusion Electrode nodes. The electronic

202 | CHAPTER 5: FUEL CELL AND ELECTROLYZER INTERFACES

conductivity, Electrical conductivity, s (SI unit: S/m), used in the domain equations,
is defined on these domains.

See also Electronic Conducting Phase Theory.

Gas Phase
The H2 Gas Phase and O2 Gas Phase nodes define the governing domain equations for
gas phase transport.

Note that these nodes are added by default, and that you cannot alter the selection of
the nodes by settings on the nodes themselves. The H2 Gas Phase and O2 Gas Phase are
active on domains selected by the corresponding H2/O2 Flow Channel, Gas
Diffusion Layer, or Gas Diffusion Electrode nodes.

The H2 Gas Phase and O2 Gas Phase subnodes are only visible if the Include gas phase
diffusion checkbox, or if the Use Darcy’s law for momentum transport checkbox, are
enabled in the corresponding Gas Mixture section on the interface top node.

COMPOSITION
Use the Mole fraction edit fields to specify the mixture composition for all gas phase
domains.

This section is only visible if any of the Include species check boxes has been selected
and the Include gas phase diffusion check box has not been selected in the interface top
node.

MIXTURE PROPERTIES
In this section, the gas phase values for the Density and Dynamic viscosity are specified.

The mixture properties will for instance be used by the interface when modeling
momentum transport by Darcy’s law.

Note: Depending on the settings on the interface top node, the mixture property
values may or may not be used by the interface itself. However, the interface will
define mixture property variables that may be used when coupling to other physics
interfaces, either manually or by multiphysics nodes such as Reacting Flow, H2/O2
Gas Phase.

THE HYDROGEN FUEL CELL AND WATER ELECTROLYZER INTERFACES | 203

 CONVECTION
This section will only be visible if the Use Darcy’s law for momentum transport check
box has been selected in the interface top node.

Specify the Velocity field of the gas. The velocity field can be specified explicitly, or
using an analytical expression, or coupled from any Fluid Flow interface, or by using
an Reacting Flow, H2/O2 Gas Phase multiphysics coupling node.

DIFFUSION
This section will only be visible if the Include gas phase diffusion check box has been
selected in the interface top node.

Specify the Binary diffusion coefficients for all pairs of species in the gas.

See also Gas Phase Theory.

Membrane
The Membrane node specifies a domain with only a Electrolyte Phase node being active.

The electrolyte conductivity of the membrane is defined on the Electrolyte Phase

node.

Current Collector
The Current Collector node specifies a domain with only the Electronic Conducting
Phase node being active.

ELECTRODE CHARGE TRANSPORT

The electronic conductivity, Electrical conductivity, s (SI unit: S/m) parameter will
define how the electric current in the corresponding Electronic Conducting Phase
domain depends on the gradient of the potential.

Gas Diffusion Layer

The H2 Gas Diffusion Layer and O2 Gas Diffusion Layer nodes specify domains where both
an Electronic Conducting Phase and a Gas Phase node are active.

204 | CHAPTER 5: FUEL CELL AND ELECTROLYZER INTERFACES

ELECTRODE CHARGE TRANSPORT
The electronic conductivity, Electrical conductivity, s (SI unit: S/m) parameter will
define how the electric current in the corresponding Electronic Conducting Phase
domain depends on the gradient of the potential.

GAS TRANSPORT
This section will only be visible if the Include gas phase diffusion check box or the Use
Darcy’s law for momentum transport checkbox has been selected in the interface top
node.

If the Include gas phase diffusion check box has been selected, the gas diffusivity defined
in the Gas Phase node will be multiplied by a correction factor to compensate for the
effect of the Gas pore volume fraction being less than 1. This can be done by either using
a Bruggeman, Tortuosity or a User defined correlation.

If the Use Darcy’s law for momentum transport checkbox has been selected, the Gas
permeability is defined in this node.

Gas Diffusion Electrode

The H2 Gas Diffusion Electrode and O2 Gas Diffusion Electrode nodes specify three phase
domains where an Electronic Conducting Phase, an Electrolyte Phase, and a Gas Phase
node are all active.

ELECTRODE CHARGE TRANSPORT

The electronic conductivity, Electrical conductivity, s (SI unit: S/m) parameter will
define how the electric current in the corresponding Electronic Conducting Phase
domain depends on the gradient of the potential.

EFFECTIVE ELECTROLYTE CHARGE TRANSPORT

The bulk electrolyte conductivity defined in the Electrolyte Phase node will be
multiplied by a correction factor to compensate for the effect of the Electrolyte volume
fraction being less than 1. This can be done by either using a Bruggeman, Tortuosity, or
User defined correlation.

GAS TRANSPORT
This section will only be visible if the Include gas phase diffusion check box or the Use
Darcy’s law for momentum transport checkbox has been selected in the interface top
node.

THE HYDROGEN FUEL CELL AND WATER ELECTROLYZER INTERFACES | 205

 If the Include gas phase diffusion check box has been selected, the gas diffusivity defined
in the Gas Phase node will be multiplied by a correction factor to compensate for the
effect of the Gas pore volume fraction being less than 1. This can be done by either using
a Bruggeman, Tortuosity, or User defined correlation.

If the Use Darcy’s law for momentum transport checkbox has been selected, the Gas
permeability is defined in this node.

Flow Channel
The H2 Gas Diffusion Layer and O2 Gas Diffusion Layer nodes specify domains with only
a Gas Phase being active.

This node will be available if the Include gas phase diffusion check box or the Use Darcy’s
law for momentum transport checkbox has been selected in the interface top node.

GAS TRANSPORT
If the Include gas phase diffusion check box has been selected, there are no settings on
this node.

If the Use Darcy’s law for momentum transport checkbox has been selected, the Gas
permeability is defined in this node.

Initial Values
Use this subnode to specify the initial values used by the solver of the dependent
variables defined by the parent node.

Initial Values, O2 Domains

Use this subnode to specify the initial values used by the solver of the dependent
variables defined by the parent Electronic Conducting Phase node.

The selection is locked to the intersection of the parent node and the O2 Gas Phase
node.

Initial Values, H2 Domains

Use this subnode to specify the initial values used by the solver of the dependent
variables defined by the parent Electronic Conducting Phase node.

206 | CHAPTER 5: FUEL CELL AND ELECTROLYZER INTERFACES

The selection is locked to the intersection of the parent node and the H2 Gas Phase
node.

Reaction Sources
This subnode is available to the Gas Phase nodes when the Advanced Physics Options is
selected in the Show More Options dialog box shown when the Show More Options
button ( ) is clicked, in combination with the checkboxes Include gas phase diffusion
or Use Darcy’s law for momentum transport being selected in the interface top node for
the corresponding gas mixture.

The node may be used for adding additional mass sources in a model, typical stemming
from non-Faradaic reactions such as water condensation-evaporation or water drag in
a low-temperature fuel cell, or homogeneous reactions such as the water gas shift
reaction in a molten carbonate fuel cell. The node contains edit fields for specifying the
reaction sources of all active gas phase species, including liquid water.

The default selection is all domains, but may be changed.

Gas Diffusion Electrode Reaction

The H2 Gas Diffusion Electrode Reaction and O2 Gas Diffusion Electrode Reaction are
available as sub nodes to the corresponding Gas Diffusion Electrode parent nodes.

The node specifies the stoichiometry, thermodynamics and kinetics of a gas diffusion
electrode reaction.

STOICHIOMETRIC COEFFICIENTS
Specify the coefficients using negative signs for oxidized species and positive signs for
reduced species. The number of electrons should always be positive.

EQUILIBRIUM POTENTIAL
The equilibrium potential may be defined using the Nernst equation, From material, or
by a User defined expression.

The Built in option for the Reference equilibrium potential is based on the reaction
stoichiometry and the enthalpies and entropies of the reacting species.

See also Calculation of Built-in Equilibrium and Thermoneutral Potentials and

Electrode Reaction in Shared Physics Features in the Current Distribution Interfaces.

THE HYDROGEN FUEL CELL AND WATER ELECTROLYZER INTERFACES | 207

 REFERENCE PRESSURES
Specify the species partial pressures for the reference state used for defining the
Reference equilibrium potential and the Reference exchange current density.

The default value (1 bar) refers to standard conditions.

ELECTRODE KINETICS
The settings of this section define how the overpotential of the electrode reaction
relates to the local current density on the (catalyst) electrode surface.

See also Electrode Reaction in Shared Physics Features in the Current Distribution
Interfaces.

ACTIVE SPECIFIC SURFACE AREA

Specify the active surface (catalyst) area available for the reaction.

HEAT OF REACTION
The settings of this section define the heat source of the reaction.

The Built in option for the Thermoneutral voltage is based on the reaction stoichiometry
and the entropies of the reacting species.

See also Calculation of Built-in Equilibrium and Thermoneutral Potentials and

Electrode Reaction in Shared Physics Features in the Current Distribution Interfaces.

Porous Double Layer Capacitance

See Porous Matrix Double Layer Capacitance in Shared Physics Features in the
Current Distribution Interfaces.

Overview of the Boundary Nodes in the Hydrogen Fuel Cell and

Water Electrolyzer Interfaces
Boundary nodes applying constraints or flux contributions to one phase only are added
as sub-nodes. The following boundary subnodes may be added to Electronic
Conducting Phase:

• Insulation (default)
• Electric Ground
• Electric Potential
• Electrode Current

208 | CHAPTER 5: FUEL CELL AND ELECTROLYZER INTERFACES

• Electrode Current Density
• Electrode Power

The following boundary subnodes may be added to Electrolyte Phase:

• Insulation (default)
• Electrolyte Potential
• Electrolyte Current Density

The following boundary subnodes may be added to H2 or O2 Gas Phase:

• No Flux (default)
• Inlet
• Outlet

The following additional boundary nodes, with contributions to multiple phases, can
be added as nodes directly under the interface node:

• Thin Gas Diffusion Electrode

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.

The node can be added as a sub node to either Electrolyte Phase or Electronic
Conducting Phase.

Electrolyte Potential
Add the Electrolyte Potential node as a subnode to the Electrolyte Phase for a boundary
with a fixed potential at a position in the electrolyte.

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

THE HYDROGEN FUEL CELL AND WATER ELECTROLYZER INTERFACES | 209

 Electrolyte Current Density
Use the Electrolyte Current Density node as a subnode to the Electrolyte Phase 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.

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

The node is typically used to ground the voltage at the current collector of the
hydrogen side of the cell.

The node can be added as a sub node to Electronic Conducting Phase.

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

 s =  s bnd

The node is typically used to set the cell voltage at the current collector of the oxygen
side of the cell.

The node can be added as a sub node to Electronic Conducting Phase.

HARMONIC PERTURBATION
Enable Include harmonic perturbation to specify the Perturbation amplitude value. This
setting will be used by the Frequency Domain Perturbation study step when running an
AC Impedance study.

Electrode Current
Use the Electrode Current node to set the total current or average current density over
an external at an external boundary of an Electronic Conducting Phase domain —
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.

210 | CHAPTER 5: FUEL CELL AND ELECTROLYZER 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) parameters.

HARMONIC PERTURBATION
Enable Include harmonic perturbation to specify the Perturbation amplitude value. This
setting will be used by the Frequency Domain Perturbation study step when running an
AC Impedance study.

Electrode Current Density

The Electrode Current Density boundary condition can be added as a sub node to and
applied at an external boundary of an Electronic Conducting Phase domain.

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.

HARMONIC PERTURBATION
Enable Include harmonic perturbation to specify the Perturbation amplitude value. This
setting will be used by the Frequency Domain Perturbation study step when running an
AC Impedance study.

Electrode Power
The Electrode Power boundary condition sets the power drawn from, or inserted to,
the cell at an external boundary of an Electronic Conducting Phase domain

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) parameters.

No Flux
The No Flux node is the default boundary condition available for exterior boundaries
of Gas Phase nodes. It should be used on boundaries across which there is no mass flux,
typically exterior solid walls where no surface reactions occur. The condition applied
for each species corresponds to

–n  ji = 0

where n denotes the outward pointing normal of the boundary.

THE HYDROGEN FUEL CELL AND WATER ELECTROLYZER INTERFACES | 211

 Inlet
The H2 Inlet and O2 Inlet nodes adds a boundary condition for an inflow boundary,
defining the composition of the mixture and the flow boundary condition.

This node is available for exterior boundaries to Gas Phase nodes.

The Mixture specification section is available if the Include gas phase diffusion checkbox
has been selected on the interface top node. The mixture composition can be specified
using the following quantities in :

• Mass fractions: i  0,i

• Mole fractions: xi  x0,i
• Molar concentrations: ci  c0,i
• Number densities, which describes the number of particles per volume: ni  n0,i
• Densities: i  0,i
• Mass flow rates: J0,i

The section requires input for all selected gas species.

The Flow boundary condition section is available if the Use Darcy’s law for momentum
transport checkbox has been selected on the interface top node. The flow inlet
condition can be specified using Pressure or Total mass flow rate.

Outlet
The H2 Outlet and O2 Outlet nodes are the preferred boundary conditions at outlets
where the species are to be transported out of the model domain. It is useful at outlets
where it is assumed that convection is the dominating effect driving the mass flow.

This node is available for exterior boundaries to Gas Phase nodes.

If the Include gas phase diffusion checkbox has been selected on the interface top node,
the boundary condition is applied to all selected gas species and corresponds to:

– n   i  Dik dk = 0
k

If the Use Darcy’s law for momentum transport checkbox has been selected on the
interface top node, the outlet Pressure can be specified.

212 | CHAPTER 5: FUEL CELL AND ELECTROLYZER INTERFACES

Thin Gas Diffusion Electrode
Use the Thin H2 Gas Diffusion Electrode or the Thin O2 Gas Diffusion Electrode nodes to
define a thin gas diffusion electrode located at a boundary between an Electrolyte
Phase, an Electronic Conducting Phase and a Gas Phase node.

The electrode assumed to be so thin that any current and species distribution effects
along the electrode thickness can be neglected.

The volumetric current density and corresponding mass sources/fluxes of the Thin
Gas Diffusion Electrode Reaction subnodes are multiplied by the Electrode Thickness
parameter, and applied as a boundary conditions.

Thin Gas Diffusion Electrode Reaction

This node can be added as a sub node to a Thin Gas Diffusion Electrode node.

Regarding the settings of the node, see Gas Diffusion Electrode Reaction.

THE HYDROGEN FUEL CELL AND WATER ELECTROLYZER INTERFACES | 213

 Theory for the Hydrogen Fuel Cell
and Water Electrolyzer Interfaces
In this chapter:

• Electronic Conducting Phase Theory

• Electrolyte Phase Theory
• Gas Phase Theory
• Calculation of Built-in Equilibrium and Thermoneutral Potentials

For general theory on electrode reactions, kinetics, as well as mass and heat sources,
see also

• Electrode Kinetics Expressions

• Equilibrium Potentials and the Nernst Equation
• Mass Fluxes and Sources Due to Electrochemical Reactions
• Joule Heating Due to Charge Transport
• Heating Due to Electrochemical Reactions

in Theory for the Current Distribution Interfaces.

For general theory on thermodynamic models, see also

• Thermodynamic Models and Theory

Electronic Conducting Phase Theory

The Electronic Conducting Phase node solves for the electric potential  s (V) as
dependent variable.

The current density in the phase, is (A/m2), is defined as (Ref. 1)

i s = –  s eff  s (5-1)

where s, eff is the effective electric conductivity (S/m).

The charge balance equation in the phase is defined as

  i s = – i v tot (5-2)

214 | CHAPTER 5: FUEL CELL AND ELECTROLYZER INTERFACES

where iv,tot (A/m3) is the sum of a volumetric current density contributions of the
electrode reactions occurring in the Gas Diffusion Electrode domains.

For Current Collector and Gas Diffusion Layer domains,

  is = 0

Electrolyte Phase Theory

The Electrolyte Phase node solves for the electric potential  l (V) as dependent
variable.

The current density in the phase, il (A/m2), is defined as (Ref. 1)

i l = –  l eff  l (5-3)

where l, eff is the effective electrolyte conductivity (S/m).

The charge balance equation in the phase is defined as

  i l = i v tot (5-4)

where iv,tot (A/m3) is the sum of a volumetric current density contributions of the
electrode reactions occurring in the Gas Diffusion Electrode domains.

For Membrane and Gas Diffusion Layer domains

  il = 0

Gas Phase Theory

GAS PHASE DIFFUSION

When gas phase diffusion is enabled, the gas phase nodes solve for a set of mass fraction
variables, i, where i is the index of the species. The governing equations are defined
using the Maxwell–Stefan set of equations, as described in Theory for the Transport of
Concentrated Species Interface.

DARCY’S LAW
When Darcy’s law is enabled, the gas phase nodes solve for a pressure variable p (Pa).

The Darcy’s law equations are documented in Theory for the Darcy’s Law Interface.

THEORY FOR THE HYDROGEN FUEL CELL AND WATER ELECTROLYZER INTERFACES | 215
 BUILT-IN BINARY DIFFUSION COEFFICIENTS
The calculation of the built-in binary diffusion coefficients is done using the Fuller–
Schettler–Giddings (FGS) model (Ref. 2):

– 2 1.75 1 1-
1.01325  10 T ------- + ------
0 Mi Mj
D i j = -------------------------------------------------------------------------------
1 1 2
- (5-5)
 --- ---
 3   3
P   v +  v 
 
  
 i  
j

where T denotes the temperature (K), Mi the molecular weight of species i (g/mol),
P is the pressure (Pa), and vi are the atomic diffusion volumes (Fuller diffusion
volume) (cm3),
TABLE 5-1: DIFFUSION VOLUMES USED FOR CALCULATING BINARY DIFFUSION COEFFICIENTS.

SPECIES FULLER DIFFUSION

VOLUME

H2 6.12
N2 18.5
O2 16.3
CO 18
CO2 26.9
H2O 13.1

BUILT-IN DYNAMIC VISCOSITY

The built-in mixture viscosity of the gas phase is based on kinetic theory by Brokaw
(Ref. 3):

 
 x 
 ---------------------
i i v 
v =  
-

i
 
 x j  i j

j

where

 i v
 i j = A i j ---------
- (5-6)
 j v

and the interaction parameter is defined as

216 | CHAPTER 5: FUEL CELL AND ELECTROLYZER INTERFACES

  
 i j  RM i j – RM i0.45 j


A i j = -------------------- 1 + ----------------------------------------------------------------------------------------- (5-7)
RM i j  1 + RM i0.45 j

2  1 + RM i j  + ------------------------------------------------
   i j   1 + RM i j 

with

 4M i M j  1 / 4 Mi
 i j =  ----------------------------2 , RM i j = ------- (5-8)
  Mi + M   Mj
j

where i,v is the vapor viscosity of each individual species, and Mi are the molecular
weights.

BUILT-IN HEAT CAPACITY

The Hydrogen Fuel Cell and Water Electrolyzer interfaces also calculate the heat
capacity of the gas mixture which may be used in heat transfer simulations. The heat
capacity is calculated as

 i c p i
C p mix =  --------------
Mi
-
i

where Cp,mix is the heat capacity of the fluid mixture in J/(kg·K), cp,i is the species
heat capacity in J/(mol·K).

Calculation of Built-in Equilibrium and Thermoneutral Potentials

The change of enthalpy for an electrode reaction is (Ref. 1)

r H =  i Hi
i

where Hi = Hi(T) are the enthalpies of formation of the reacting species of index i, and
i the stoichiometric coefficients.

Similarly, the change of entropy is

r S =  i Si
i

Where Si = Si(T) is the (absolute) molar entropy.

THEORY FOR THE HYDROGEN FUEL CELL AND WATER ELECTROLYZER INTERFACES | 217
 Hi and Si are generally known for liquids and gases, whereas for ions the values will
depend on the nature of the electrolyte in use, and are hence hard to measure
experimentally.

The corresponding change of Gibbs free energy of a reaction is

 r G =  r H – T r S

The equilibrium potential for an electrode reaction is

–r G
E eq = --------------
nF

and the thermoneutral voltage, required to compute electrode reaction heat sources, is

–r H
E therm = --------------
nF

where n is the number of electrons included in the electrode reaction.

Temperature dependent thermodynamic expressions for gaseous species of Hi(T) and

Si(T), at standard partial pressures of 1 atm, are based on Ref. 5.

For the charge-conducting ion in the electrolyte, entropy and enthalpy values are
however generally not known and need to be set by the user. The stochiometric
coefficient of the charge-carrying ion is derived from the number of electrons
participating in the charge transfer reaction and the charge carrying ion charge as

n
 ion = – ---------
z ion

For convenience, the built-in equilibrium potentials are defined versus a reversible
reference hydrogen electrode (RHE) for the same electrolyte type, for a specified
reference temperature. This will have the effect that the HOR/HER will have an
equilibrium potential in a model close to 0 V, and the ORR/OER reaction will have
an equilibrium potential ranging from around 1.2 (at room temperature) to 1.0 V (at
800°C). This shift facilitates setting for instance initial values for the potential
dependent variables in a model.

The reference equilibrium and thermoneutral potentials used by the electrode reaction
node, versus the RHE, are defined as

–  r G ref
E eq ref = -------------------- – E eq RHE
nF

218 | CHAPTER 5: FUEL CELL AND ELECTROLYZER INTERFACES

and

–r H
E therm = -------------- – E eq RHE
nF

where

 r G ref =  r H – T r S ref

with Sref being the change in entropy at the chosen reference conditions (typically
1 atm).

Note that due to cancellation in the equation for Eeq, ref, the values of the ion entropy
(0 by default) has no impact on the equilibrium potentials values (nor the overall cell
voltage and energy balance), but it will impact how the thermoneutral voltage Etherm
and corresponding heat sources for the individual electrode reactions are computed.

LIQUID WATER THERMODYNAMIC EXPRESSIONS AND RELATIVE

HUMIDITY
The fc/we interface defines the water vapor pressure, pvap (Pa), and the enthalpy of
vaporization Hvap (J/mol), by the use of an experimental correlations (interpolation)
functions vs temperature. The pvap(T) correlation is based on Ref. 4, whereas Hvap(T)
is defined using the same source data as in the Thermodynamics node (See Using
Thermodynamic Properties).

The enthalpy of formation of liquid water, HH2O(l) (J/mol), is then defined as

H H2O(l) = H H2O(g) – H vap

Assuming the vapor the behave as an ideal gas, and the liquid water to be
incompressible, the following equation for the entropy of liquid water can be derived

p vap H vap
S H2O(l) = – R ln ----------- – ------------- + S H2O(g)
p ref T

The relative humidity, RH (1), is defined as

p vap
RH = -----------
p ref

THEORY FOR THE HYDROGEN FUEL CELL AND WATER ELECTROLYZER INTERFACES | 219
 References
1. J. Newman and K. Thomas-Alyea, “Electrochemical Systems”, John Wiley & Sons
2004.

2. E.N. Fuller, P.D. Schettler, and J.C. Giddings, “A new method for prediction of
binary gas-phase diffusion coefficients,” Industrial and Engineering Chemistry,
vol. l 5, pp. 19–27, 1966.

3. R.S. Brokaw, “Approximate formulas for the viscosity and thermal conductivity of
gas mixtures. ii,” Journal of Chemical Physics, vol. 42, no. 4, pp. 1140–1147, 1965.

4. HJ Kretzschmar, W. Wagner, International Steam Tables, Properties of Water and

Steam based on the Industrial Formulation IAPWS-IF97, 3rd Edition, 2019,
Springer-Verlag GmbH Germany

5. MW Chase, “NIST-JANAF Themochemical Tables, Fourth Edition”, J. Phys.

Chem. Ref. Data, Monograph 9, 1998, 1-1951

220 | CHAPTER 5: FUEL CELL AND ELECTROLYZER INTERFACES

 6

Chemical Species Transport Interfaces

This chapter describes the physics interfaces found under the Chemical Species
Transport branch ( ).

In this chapter:

• The Transport of Diluted Species Interface

• The Transport of Concentrated Species Interface
• The Chemistry Interface
• The Nernst-Planck-Poisson Equations Interface
• The Electrophoretic Transport Interface
• The Surface Reactions Interface
• The Reacting Flow Interfaces
• The Reacting Flow in Porous Media Interfaces

The theory for all the interfaces is also discussed at the end of the chapter and links
are included with the interfaces.

221
 T he T r a ns po r t of D i l u t ed S p ec i es
Interface
The Transport of Diluted Species (tds) interface ( ), found under the Chemical Species
Transport branch ( ), is used to calculate the concentration field of a dilute solute in
a solvent. Transport and reactions of the species dissolved in a gas, liquid, or solid can
be handled with this interface. The driving forces for transport can be diffusion by
Fick’s law, convection when coupled to a flow field, and migration, when coupled to
an electric field.

The interface supports simulation of transport by convection and diffusion in 1D, 2D,
and 3D as well as for axisymmetric components in 1D and 2D. The dependent variable
is the molar concentration, c. Modeling multiple species transport is possible, whereby
the physics interface solves for the molar concentration, ci, of each species i.

SETTINGS
The Label is the default physics interface name.

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

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

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

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

222 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Note: Some of the additional transport mechanisms listed below are only available in
certain products. For details see https://www.comsol.com/products/specifications/.

• By default, the Convection check box is selected. Clear the check box to disable
convective transport.
• Select the Migration in electric field check box to activate transport of ionic species in
an electric field. See further the theory section Adding Transport Through
Migration.

Transport of ionic species in an electric field is available in a limited set of

add-on products. See https://www.comsol.com/products/
specifications/ for more details on availability.

Mass Transport in Porous Media

The Mass transport in porous media check box activates functionality specific to species
transport in porous media:

• 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 https://www.comsol.com/products/
specifications/ for more details on availability.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 223

 CONSISTENT STABILIZATION
To display this sections, click the Show button ( ) and select Stabilization.

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

INCONSISTENT STABILIZATION
To display this section, click the Show button ( ) and select Stabilization. By default,
the Isotropic diffusion check box is not selected, because this type of stabilization adds
artificial diffusion and affects the accuracy of the original problem. However, this
option can be used to get a good initial guess for 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

224 | CHAPTER 6: 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 | 225

 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

226 | CHAPTER 6: 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: https://www.comsol.com/model/
variably-saturated-flow-and-transport-sorbing-solute-490

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 227

 Domain, Boundary, and Pair Nodes for the Transport of Diluted
Species 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.

228 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

Some features require certain add-on modules. For details see https://
www.comsol.com/products/specifications/

For axisymmetric components, COMSOL Multiphysics takes the axial

symmetry boundaries (at r  0) into account and automatically adds an
Axial Symmetry node that is valid on boundaries representing the
symmetry axis.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 229

 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.

When the Convection check box is selected, the Turbulent Mixing subnode is available
from the context menu as well as from the Physics toolbar, Attributes menu.

MODEL INPUTS
The temperature model input is always available. Select the source of the Temperature.
For User defined, enter a value or expression for the temperature in the input field. This
input option is always available.

You can also select the temperature solved for by a Heat Transfer interface added to
the model component. These physics interfaces are available for selection in the
Temperature list.

CONVECTION
If transport by convection is active, the velocity field of the solvent needs to be
specified. Select the source of the Velocity field. For User defined, enter values or
expressions for the velocity components in the input fields. This input option is always
available.

You can also select the velocity field solved for by a Fluid Flow interface added to the
model component. These physics interfaces are available for selection in the Velocity
field list.

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

230 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

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:/
/www.comsol.com/products/specifications/.

MIGRATION IN ELECTRIC FIELD

This section is available when the Migration in electric field check box is selected. From
the Electric potential list, select the source of the electric field.

• Enter a value or expression for the Electric potential V, which is User defined; this
input option is always available.
• Select the electric potential solved by an AC/DC-based interface that has also been
added to the model.
• Select the electric potential defined or solved by Electrochemistry interface that has
been added to the component.

By default the Mobility is set to be calculated based on the species diffusivity and the
temperature using the Nernst-Einstein relation. For User defined, and under Mobility,
select the appropriate scalar or tensor type — Isotropic, Diagonal, Symmetric, or 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 TRANSPORT OF DILUTED SPECIES INTERFACE | 231

 The temperature (if you are using mobilities based on the Nernst-Einstein relation) is
taken from Model Inputs section.

Note that the migration in electric fields feature is only available in some COMSOL
products. See details: https://www.comsol.com/products/specifications/.

EXAMPLE MODELS

• Separation Through Dialysis: Application Library path

Chemical_Reaction_Engineering_Module/Mixing_and_Separation/dialysis
Web link: https://www.comsol.com/model/
separation-through-dialysis-258

• Transport in an Electrokinetic Valve: Application Library path

Microfluidics_Module/Fluid_Flow/electrokinetic_valve
Web link: https://www.comsol.com/model/electrokinetic-valve-603

Turbulent Mixing
Use this node to account for the turbulent mixing of the chemical species caused by
the eddy diffusivity. This node should typically be used when the specified velocity field
corresponds to a RANS solution.

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

https://www.comsol.com/products/specifications/ for more details on
availability.

The subnode can added from the context menu (right-click the Transport Properties
parent node), as well as from the Physics toolbar, Attributes menu, provided that
Convection is selected as a transport mechanism.

TURBULENT MIXING PARAMETERS

Some physics interfaces provide the turbulent kinematic viscosity, and these appear as
options in the Turbulent kinematic viscosity T list. The list always contains the User
defined option where any value or expression can be entered.

The default Turbulent Schmidt number ScT is 0.71 (dimensionless).

232 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

FURTHER READING
See the section About Turbulent Mixing in the CFD Module User’s Guide (this link
is available online or if you have the CFD Module documentation installed).

Initial Values
The Initial Values node specifies the initial values for the concentration of each species.
These serve as an initial guess for a stationary solver or as initial conditions for a
transient simulation.

DOMAIN SELECTION
If there are several types of domains with different initial values defined, it might be
necessary to remove some domains from the selection. These are then defined in an
additional Initial Values node.

INITIAL VALUES
Enter a value or expression for the initial value of the Concentration or concentrations,
ci. This also serves as a starting guess for stationary problems.

Mass-Based Concentrations
Use the Mass-Based Concentrations node to add postprocessing variables for mass-based
concentrations (SI unit: kg/m3) and mass fractions (dimensionless) for all species.

MIXTURE PROPERTIES
The default Solvent density solvent 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.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 233

 REACTION RATES
Add a rate expression R (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 https://www.comsol.com/products/specifications/ for
more details on availability.

When specifying reaction rates for a species in porous media, the specified reaction rate
may have the basis of the total volume, the pore volume, or the volume of a particular
phase.

• For Total volume, the reaction expressions in mol/(m3·s) are specified per unit
volume of the model domain (multiplied by unity).
• For Pore volume, the reaction expressions in mol/(m3·s) are specified per unit
volume of total pore space. The reaction expressions will be multiplied by the
domain porosity, p. (p equals unity for nonporous domains.)
• For Liquid phase, the reaction expressions in mol/(m3·s) are specified per unit
volume of liquid in the pore space. The expressions will be multiplied by the liquid
volume fraction . ( equals p for Saturated Porous Media domains).
• For Gas phase, the expressions are multiplied by the gas volume fraction av  p  
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: https://www.comsol.com/model/
fine-chemical-production-in-a-plate-reactor-8589

234 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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  = 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

or

– n   – Dc – zu m Fc + 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.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 235

 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 .

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

236 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

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  = 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  .

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

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 237

 – n   – Dc – zu m Fc + 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 

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:

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

238 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

condition for a specific species, click to clear the check box for the flux discontinuity
of that species.

Partition Condition
The Partition Condition node can be used to prescribe the ratio between the
concentration of a solute species in two different immiscible phases. It can for example
be used on interior boundaries separating two liquid phases, a gas-liquid interface, or
on a boundary separating a liquid phase and a solid or porous media. For a species
concentration ci, the ratio between the concentration on the up side and on the down
side of the boundary (ci,u and ci,d respectively) is defined as

c i u
K i = ---------
c i d

in terms of a partition coefficient Ki. The up and down side of the selected boundary
is indicated in the Graphics window. The arrows point from the down side into the up
side.

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

https://www.comsol.com/products/specifications/ for more details on
availability.

PARTITION COEFFICIENT
Select the Reverse direction check box to reverse the direction of the arrows on the
selected boundaries, and the corresponding definition of the up and down side
concentration.

Use the associated input fields to prescribe the partition coefficient Ki.

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

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 239

 Periodic Condition
The Periodic Condition node can be used to define periodicity for the mass transport
between two sets of boundaries. The node prescribes continuity in the concentration
and the mass flux between the “source” and the “destination” side respectively. Note
that these names are arbitrary and does not influence the direction in which mass is
transported. It is dictated by mass transfer equations in the adjacent domains.

The node can be activated on more than two boundaries, in which case the feature tries
to identify two separate surfaces that each consist of one or several connected
boundaries.

For more complex geometries, it might be necessary to add the Destination Selection
subnode, which is available from the context menu (right-click the parent node) as well
as from the Physics toolbar, Attributes menu. With this subnode, the boundaries that
constitute the source and destination surfaces can be manually specified.

FURTHER READING
For an example of using a periodic condition, see this application example:

The KdV Equation and Solitons: Application Library path

COMSOL_Multiphysics/Equation_Based/kdv_equation

Line Mass Source

The Line Mass Source feature models mass flow originating from a tube or line region
with an infinitely small radius.

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

https://www.comsol.com/products/specifications/ for more details on
availability.

240 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

SELECTION
The Line Mass Source feature is available for all dimensions, but the applicable selection
differs between the dimensions.

MODEL DIMENSION APPLICABLE GEOMETRICAL ENTITY

2D Points
2D Axisymmetry Points not on the symmetry axis and the symmetry axis
3D Edges

SPECIES SOURCE
ꞏ
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.

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

https://www.comsol.com/products/specifications/ for more details on
availability.

SPECIES SOURCE
ꞏ
Enter the source strength, q p,c , for each species (SI unit: mols). A positive value
results in species injection from the point into the computational domain, and a
negative value means that the species is removed from the computational domain.

Point sources located on a boundary or on an edge affect the adjacent computational

domains. This has the effect, for example, that the physical strength of a point source
located in a symmetry plane is twice the given strength.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 241

 Open Boundary
Use this node to set up mass transport across boundaries where both convective inflow
and outflow can occur. On the parts of the boundary where fluid flows into the
domain, an exterior species concentration is prescribed. On the remaining parts, where
fluid flows out of the domain, a condition equivalent to the Outflow node is instead
prescribed.

The direction of the flow across the boundary is typically calculated by a fluid flow
interface and is provided as a model input to the Transport of Diluted Species
interface.

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

https://www.comsol.com/products/specifications/ for more details on
availability.

EXTERIOR CONCENTRATION
Enter a value or expression for the Exterior concentration.

Thin Diffusion Barrier

Use this boundary condition to model a thin layer through which mass is transported
by diffusion only. The node is applicable on interior boundaries and can be used to
avoid meshing thin structures.

THIN DIFFUSION BARRIER

Specify the Layer thickness, ds, and input a Diffusion coefficient, Ds,c, for each of the
species included.

Thin Impermeable Barrier

This feature models a thin mass transfer barrier. It is available on interior boundaries
and introduces a discontinuity in the concentration across the boundary. On each side,
a no-flux condition is prescribed for the mass transport implying that it acts as a barrier.
The feature can be used to avoid meshing thin structures.

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.

242 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Equilibrium Reaction
Use this node to model a reaction where the kinetics is assumed 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.

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
https://www.comsol.com/products/specifications/ for more details
on availability.

EQUILIBRIUM CONDITION
The list defaults to Equilibrium constant or select User defined. For either option, the
Apply equilibrium condition on inflow boundaries check box is selected by default.

For Equilibrium constant, enter an Equilibrium constant Keq (dimensionless). 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 coefficientc (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.

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

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 243

 species participating in a surface reaction, the boundary flux corresponds to the
reaction rate at the surface.

SURFACE REACTION RATE

Specify the surface reaction rate J0 of each species resulting from the reactions. Note
that if you have the Chemistry interface available, provided with the Chemical
Reaction Engineering Module, the reaction rate expressions can be automatically
generated and picked up using the drop-down menu.

FURTHER READING
For an example of using the Surface Reactions node, see this application example:

Chemical Vapor Deposition of GaAs: Application Library path

Chemical_Reaction_Engineering_Module/
Reactors_with_Mass_and_Heat_Transfer/gaas_cvd

Surface Equilibrium Reaction

Use this node to model an equilibrium reaction on a boundary (surface). The settings
for this node are similar to Equilibrium Reaction. Note that a necessary requirement
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

https://www.comsol.com/products/specifications/ for more details on
availability.

Fast Irreversible Surface Reaction

This boundary node defines an irreversible reaction where the kinetics is so fast that
the only factor limiting the reaction rate is the transport of a species to the reacting
surface.

244 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

https://www.comsol.com/products/specifications/ for more details on
availability.

Porous Electrode Coupling

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

https://www.comsol.com/products/specifications/ for more details on
availability.

Reaction Coefficients
Add this node to the Electrode Surface Coupling and Porous Electrode Coupling
features to define molar fluxes and sources based on electrode current densities in an
Electrochemistry interface.

The molar flux or source is proportional to the stoichiometric coefficients and the
current density according to Faraday’s law.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 245

 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.

Electrode Surface Coupling

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

https://www.comsol.com/products/specifications/ 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

https://www.comsol.com/products/specifications/ for more details on
availability.

246 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Species transport through a porous medium is affected both by properties of 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, 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.

Fluid
Use this node to specify the mass transfer in the mobile fluid solvent filling the pores
of the 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.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 247

 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 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 F,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:/
/www.comsol.com/products/specifications/.

MIGRATION IN ELECTRIC FIELD

This section is available when the Migration in electric field check box is selected. From
the Electric potential list, select the source of the electric field.

• 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.

248 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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 p 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

p = 1 –  s i – imf i
i i

where s,i and imf,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 b and the (single phase) Pellet density pe. The porosity is then defined from

b
 p = 1 – --------
 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

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 249

 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.

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

https://www.comsol.com/products/specifications/ 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, 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

250 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

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 l = ps.

For Liquid volume fraction, enter a value for l (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 d/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.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 251

 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
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 L,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:
https://www.comsol.com/products/specifications/.

MIGRATION IN ELECTRIC FIELD

This section is available when the Migration in electric field check box is selected. From
the Electric potential list, select the source of the electric field.

• 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.

252 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

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

https://www.comsol.com/products/specifications/ 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 , or the Solid phase
density s. 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 | 253

 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 NT
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
cS

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):

254 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 cP = f  c 

For more information, see in the theory section.

FURTHER READING
See the theory chapter in the section .

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

https://www.comsol.com/products/specifications/ for more details on
availability.

VOLATILIZATION
Enter a Mass transfer coefficient hc defining the transfer into the surrounding media.
This can be given by boundary layer theory. When assuming that no convective flow
is present in the surrounding, the mass transfer coefficient can be defined from the gas
diffusion coefficient DGc and the thickness of the diffusion layer ds in the manner of

D Gc
h c = ----------
ds

Also give the atmospheric concentration for each species, cGatm,c. The Volatilization
coefficient kG,c for each species are taken from the adjacent Unsaturated Porous
Medium domain.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 255

 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

 hs =  h M m  c mo – c mo,ref 

where h 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://
www.comsol.com/products/specifications/.

256 | CHAPTER 6: 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.

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

https://www.comsol.com/products/specifications/ for more details on
availability.

FRACTURE PROPERTIES
Specify a value for the Fracture thickness dfr.

MATRIX PROPERTIES
Use the Porous material list to define a material specifying the matrix properties on the
current selection. By default the Boundary material is used.

Specify the Porosity, p (dimensionless) of the porous matrix. This is by default taken
From material. Select User defined to instead enter a different value.

CONVECTION
Select an option from the Velocity field list to specify the convective velocity along the
fracture. For a consistent model, use a Fracture Flow feature in a Darcy’s Law interface
to compute the fluid flow velocity in the fracture.

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

The settings for the Diffusion 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.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 257

 The Transport of Diluted Species in
Fractures Interface
The Transport of Diluted Species in Fractures (dsf) interface ( ), found under the
Chemical Species Transport branch ( ), is used to model the transport of a solute
species along thin porous fractures, taking into account diffusion, dispersion,
convection, and chemical reactions. The fractures are defined by boundaries and the
solute species is assumed to be present in a solvent.

The interface supports simulation of species transport along boundaries in 2D and 3D,
and axisymmetric components in 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.

This interface is only available in a limited set of add-on products. For a

detailed overview of which interfaces are available in each product, visit
https://www.comsol.com/products/specifications/

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 dsf.

BOUNDARY SELECTION
If model geometry includes boundaries that should not be included in the mass
transfer simulation, remove those from the selection list.

TRANSPORT MECHANISMS
Mass transport due to diffusion is always included. Use the Convection check box,
available under Additional transport mechanisms, to control whether to also include
convective transport.

258 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

CONSISTENT STABILIZATION
To display this sections, click the Show button ( ) and select Stabilization. Use this
section to control the application of the available consistent stabilization methods;
Streamline diffusion and Crosswind diffusion.

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

INCONSISTENT STABILIZATION
To display this section, click the Show button ( ) and select Stabilization. By default,
the Isotropic diffusion check box is not selected, because this type of stabilization adds
artificial diffusion and affects the accuracy of the original problem. However, this
option can be used to get a good initial guess for under resolved problems.

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

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.

THE TRANSPORT OF DILUTED SPECIES IN FRACTURES INTERFACE | 259

 DEPENDENT VARIABLES
The dependent variable name is Concentration c by default. A dependent variable name
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.

FURTHER READING

• Mass Transport in Fractures in the theory section.

• Numerical Stabilization in the COMSOL Multiphysics Reference
Manual.
• 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 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.

Boundary, Edge, Point, and Pair Nodes for the Transport of Diluted
Species in Fractures Interface
The Transport of Diluted Species in Fractures Interface has the following 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 by
right-clicking to access the context menu (all users).

• Adsorption • Initial Values

• Concentration • No Flux
• Flux • Outflow
• Fracture • Reactions
• Inflow • Species Source

260 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Adsorption
Use this node to model adsorption of the fluid phase species onto the porous media
surface of the fracture.

MATRIX PROPERTIES
Use the Porous material list to define a material specifying the matrix properties on the
current selection. By default the Domain material is used. The density of the porous
media is needed when modeling adsorption to the surface of the porous matrix. By
default Density  is set to from domain material.

ADSORPTION
Select an Adsorption isotherm — Langmuir (the default), 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:

KL c c P K L c Pmax
c P = c Pmax -------------------- -------- = ---------------------------
1 + KL c c  1 + KL c 
2

Enter a Langmuir constant kL,c (SI unit: m3/mol) and an Adsorption maximum
cp,max,c (SI unit: mol/kg):

• For Freundlich:

c N c P c
c P = K F  -------- -------- = N ----P- Freundlich
 c ref c c

Enter a Freundlich constant kF,c (SI unit: mol/kg), a Freundlich exponent NF,c
(dimensionless), and a Reference concentration cref,c (SI unit: mol/m3).

• For Toth:
bT c
c P = c Pmax ----------------------------------------------
N 1  NT
 1 +  bT c  T 

and

THE TRANSPORT OF DILUTED SPECIES IN FRACTURES INTERFACE | 261

 –  1 + -------
1
c P N
 N T
-------- = 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
cS

and

2 2
K B c 0 c S   K B – 1 c + c S 
-----------------------------------------------------------------
-
2 2
 c – c S   c S +  K B – 1 c 

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:

cP = f  c 

Enter an adsorption isotherm cP,c (SI unit: mol/kg).

For more information, see Adsorption.

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

Concentration
Use this node to specify the species concentration on a fracture boundary (applied in
points in 2D and along edges in 3D). 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

262 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

corresponding field. To use another boundary condition for a specific species, click to
clear the check box for the concentration of that species.

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.
You can find details about the different constraint settings in the section Constraint
Reaction Terms in the COMSOL Multiphysics Reference Manual.

Flux
This node can be used to specify the species flux across a boundary of a porous fracture
(applied in points in 2D and along edges in 3D). The flux of species c is defined as

n   D e c  = N 0

where N0 is an arbitrary user-specified flux expression. For example, N0 can represent

a flux due to chemical reactions, or a phase change. A positive N0 implies that the
concentration inside the fracture increases.

INWARD FLUX
Specify the flux of each species individually. To use another boundary condition for a
specific species, click to clear the check box for the mass fraction of that species.

Fracture
Use this node to model mass transport along thin fracture surfaces situated inside
porous or solid material. The node assumes that the transport in the tangential
direction of the fracture is dominant, as a result of lower flow resistance. Note that the
fracture it self is modeled as porous.

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, p (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 The Fracture Flow Interface (available with the

THE TRANSPORT OF DILUTED SPECIES IN FRACTURES INTERFACE | 263

 Subsurface Flow Module and the Porous Media Flow Module) to compute the fluid
flow velocity.

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.

Inflow
Use this node to specify all species concentrations at a fracture inlet. The condition is
applied in points in 2D and along edges in 3D.

If you want to specify the concentration of a subset of the partaking species, this can
be done by using the Concentration node instead.

CONCENTRATION
For the concentration of each species c0,c (SI unit: mol/m3), enter a value or
expression.

BOUNDARY CONDITION TYPE

This section in the settings is only available for some products. Search for “Inflow” on
the page: https://www.comsol.com/products/specifications/ for more details on
availability.

The option Concentration constraint constrains the concentration values on the

boundary by the use of pointwise constraints. The other option, Flux (Danckwerts) can
be more stable and fast to solve when high reaction rates are anticipated in the vicinity
of the inlet. Oscillations on the solutions can also be avoided in such cases. The latter
condition uses a flux boundary condition based on the velocity across the boundary
and the concentration values. See further details in the theory section.

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.
You can find details about the different constraint settings in the section Constraint
Reaction Terms in the COMSOL Multiphysics Reference Manual.

264 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

FURTHER READING
See the theory chapter in the section Danckwerts Inflow Boundary Condition.

No Flux
This node can be used to specify that the species flux across a boundary of a porous
fracture is zero. The condition is applied in points in 2D and along edges in 3D.

Outflow
Set this condition at fracture outlets where species are transported out of the model
domain by fluid motion. The condition is applied in points in 2D and along edges in
3D. It is assumed that convection is the dominating transport mechanism across
outflow boundaries, and therefore that diffusive transport can be ignored, that is:

n   – D e c  = 0

Reactions
Use the Reactions node to account for the consumption or production of species
through chemical reactions in the fracture. Define the rate expressions as required.

BOUNDARY SELECTION
From the Selection list, choose the boundaries 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
of the fracture.

REACTION RATES
Add a rate expression Ri 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.

THE TRANSPORT OF DILUTED SPECIES IN FRACTURES INTERFACE | 265

 REACTING VOLUME
When specifying reaction rates for a species in a fracture, the specified reaction rate may
have the basis of the pore volume of the fracture, or the total volume.

• For Total volume, the reaction expressions in are specified per unit volume of the
fracture. The reaction expressions will be multiplied by the fracture thickness dfr.
• For Pore volume, the reaction expressions in mol/(m3·s) are specified per unit
volume of total pore space in the fracture. The reaction expressions will be
multiplied by the fracture thickness dfr and the fracture porosity, p.

Species Source
In order to account for consumption or production of species in a fracture, the Species
Source node adds source terms expressions Si to the right-hand side of the species
transport equations.

BOUNDARY SELECTION
From the Selection list, choose the boundaries on which to define expressions that
govern the source term in the transport equations.

If there are several different parts of the fracture, with subsequent and different sources
occurring within them, it might be necessary to remove some boundaries from the
selection. The sources in these can then be defined using an additional Species Source
node.

SPECIES SOURCE
Add a source term Si for each of the species solved for. Enter a value or expression in
the field of the corresponding species.

266 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

T he T r a ns po r t of Con cen t rat ed
S pe c i e s I nte r fac e
The Transport of Concentrated Species (tcs) interface ( ), found under the Chemical
Species Transport branch ( ) when adding a physics interface, is used to study
gaseous and liquid mixtures where the species concentrations are of the same order of
magnitude and none of the species can be identified as a solvent. In this case, properties
of the mixture depend on the composition, and the molecular and ionic interactions
between all species need to be considered. The physics interface includes models for
multicomponent diffusion, where the diffusive driving force of each species depends
on the mixture composition, temperature, and pressure.

The physics interface solves for the mass fractions of all participating species. Transport
through convection, diffusion, and migration in an electric field can be included.

It supports simulations of transport by convection, migration, and diffusion in 1D,

2D, and 3D as well as for axisymmetric components in 1D and 2D. The physics
interface defines the equations for the species mass fractions, including a diffusion
model (Mixture-averaged, Maxwell–Stefan, or Fick’s law).

The available transport mechanisms and diffusion models differs between various
COMSOL products (see https://www.comsol.com/products/specifications/).

Some examples of what can be studied with this physics interface include:

• The evolution of a chemical species transported by convection and diffusion.

• The migration in an electric field in the case of ionic species, in mixtures and
solutions that cannot be deemed as being diluted.
• Concentrated solutions or gas mixtures, where the concentration of all participating
species are of the same order of magnitude, and their molecular and ionic interaction
with each other therefore must be considered. This implies that the diffusive
transport of a single species is dependent on the mixture composition, and possibly
on the temperature, the electric potential, the pressure, or any combination.

When this physics interface is added, the following default nodes are also added in the
Model Builder — Transport Properties, No Flux, and Initial Values. Then, from the Physics
toolbar, add other nodes that implement, for example, boundary conditions and
reactions. You can also right-click Transport of Concentrated Species to select physics
features from the context menu.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 267

 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 tcs.

EQUATION
The basic equation for the conservation of mass of a species i is:

 
 i  +     i u  = –   j i + R i (6-1)
t

Using the continuity equation, the sum of all species equations, the equation can be
re-cast in its non-conservative form:


 ( i) +   u    i = –   j i + R i (6-2)
t

The form of the equation is the one which is used the Transport of Concentrated
Species interface. The equation displayed in the interface changes depending on the
active transport mechanisms, the selected diffusion model, and the type of reactions
modeled.

TRANSPORT MECHANISMS
The Transport of Concentrated Species interface always accounts for transport due to
diffusion.

The available diffusion models and the additional transport mechanisms differs
between various COMSOL products (see https://www.comsol.com/products/
specifications/).

Diffusion Model
• The Maxwell–Stefan option employs the most detailed diffusion model, but is also
the most computationally expensive. The model is intended for diffusion dominated
models, and requires that the multicomponent Maxwell–Stefan diffusivities of all
component pairs are known. No stabilization is available when selecting this model.

268 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

• The Mixture-averaged option is less computationally expensive than the Maxwell–
Stefan model. It is a simpler model that can be used when variations in the partial
pressures and temperature can be assumed to not affect the multicomponent
diffusion. The model includes stabilization but requires the multicomponent
Maxwell–Stefan diffusivities of all component pairs.
• The Fick’s law model is a general model that should be used when the diffusion is
assumed Fickian, or when no multicomponent diffusivities are available. Also, when
molecular diffusion is not the dominating transport mechanism and a robust but
low order model is wanted, the Fick’s law options should be used. The model
includes stabilization.

Additional Transport Mechanisms

Under Additional transport mechanisms, click to select or clear any combination of
check boxes as needed.

Migration in Electric Field

Select the Migration in electric field check box to activate migration of ionic species due
to an electric field. The resulting migration term is part of the relative mass flux vector.

Mass Transport in Porous Media

The Mass transport in porous media check box activates functionality specific to species
transport in porous media. When selected the following features are enabled:

• Porous Media Transport Properties

• Porous Electrode Coupling

Knudsen Diffusion
For Mixture-averaged and Fick’s law, it is possible to include Knudsen diffusion. This
mechanism accounts for species collisions with the surrounding media, for example,
the pore walls the species pass through. It is also an important component when setting
up a Dusty gas model.

Maxwell–Stefan Diffusion Model

When using the Maxwell–Stefan diffusion model the relative mass flux vector is

Q T
Di
j i = –  i  D̃ ik d k – -------- T
T
k=1

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 269

 ˜
where D ik (SI unit: m2/s) are the multicomponent Fick diffusivities, dk (SI unit: 1/
T
m) is the diffusional driving force, T (SI unit: K) is the temperature, and D i (SI
unit: kg/(m·s)) is the thermal diffusion coefficient.

The diffusional driving force is defined as

Q
1
d k = x k + ---  x k –  k  p –  k g k +  k
p  l gl (6-3)
l=1

where gk is an external force (per unit mass) acting on species k. In the case of an ionic
species, the external force due to the electric field, which is added by selecting the
Migration in electric field check box, is

zk F
g k = – ---------  (6-4)
Mk

where zk is the species charge number, F (SI unit: A·s/mol) is Faraday’s constant and
 (SI unit: V) is the electric potential.

Mixture-Averaged Diffusion Model

When using the Mixture-averaged diffusion model, the diffusive flux is formulated in
terms of a mixture-averaged diffusion coefficient representing the diffusion of each
species into the resulting mixture. The diffusion coefficient is based on the
multicomponent Maxwell–Stefan diffusivities Dik. The Mixture-averaged diffusion
model is computationally less expensive, and significantly more robust than the
Maxwell–Stefan Diffusion Model, but constitutes an approximation of the
multicomponent flux. For information on the flux formulation in this case see
Multicomponent Diffusion: Mixture-Averaged Approximation.

Fick’s Law Diffusion Model

When using the Fick’s law diffusion model, the diffusive flux is formulated in terms of
a Fickian diffusion coefficient. The Fick’s law diffusion model is computationally less
expensive and significantly more robust than the Maxwell–Stefan Diffusion Model, but
constitutes an approximation of the multicomponent flux. For information on the flux
formulation in this case see Multispecies Diffusion: Fick’s Law Approximation.

SPECIES
Select the species that this physics interface solves for using the mass constraint in
Equation 6-38 (that is, its value comes from the fact that the sum of all mass fractions
must equal 1). In the From mass constraint list, select the preferred species. To

270 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

minimize the impact of any numerical and model introduced errors, use the species
with the highest concentration. By default, the first species is used.

1 = 1 –  i (6-5)
i=2

CONSISTENT AND INCONSISTENT STABILIZATION

To display this section, click the Show button ( ) and select Stabilization.

• There are two consistent stabilization methods available when using the
Mixture-Averaged Diffusion Model or Fick’s Law Diffusion Model — Streamline
diffusion and Crosswind diffusion. Both are active by default.
The Residual setting applies to both the consistent stabilization methods.
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 computationally faster. If required, select Full residual instead.
• There is one inconsistent stabilization method, Isotropic diffusion, which is available
when using the Mixture-Averaged Diffusion Model or Fick’s Law Diffusion Model.

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

Regularization
From the Regularization list, select On (the default) or Off. When turned On, regularized
mass fractions are calculated such that

0  w i reg  1

Regularized mass fractions are used for the calculation of composition-dependent

material properties, such as the density.

Diffusion
The Diffusion settings are available for the approximate diffusion models
Mixture-averaged and Fick’s law.

When the Mixture diffusion correction is enabled, a flux correction is added to ensure
that the net diffusive flux is zero. This typically also mean that the solution becomes
less sensitive to the species selected to be computed from the mass constraint in the

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 271

 Species section. More information on this correction is available in the theory section
Multicomponent Diffusion: Mixture-Averaged Approximation.

The Diffusion flux type list controls the whether the molecular flux is assumed
proportional to the mole fraction or the mass fraction. See Multicomponent Diffusion:
Mixture-Averaged Approximation or Multispecies Diffusion: Fick’s Law
Approximation for information on the diffusive flux formulation.

Pseudo Time Stepping

The Use pseudo time stepping for stationary equation form option adds pseudo time
derivatives to the equation when the Stationary equation form is used in order to speed
up convergence. When selected, a CFL number expression should also be defined. For
the default Automatic option, the local CFL number (from the Courant–Friedrichs–
Lewy condition) is determined by a PID regulator. For more information, see Pseudo
Time Stepping for Mass Transport.

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

For more information about these settings, see the Discretization section under 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.

• Domain, Boundary, and Pair Nodes for the Transport of Concentrated

Species Interface
• Theory for the Transport of Concentrated Species Interface

• 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
Web link: https://www.comsol.com/model/
species-transport-in-the-gas-diffusion-layers-of-a-pem-260

272 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

DEPENDENT VARIABLES
Add or remove species in the model and also change the names of the dependent
variables that represent the species concentrations.

Specify the Number of species. There must be at least two species. To add a single
species, click the Add concentration button ( ) under the table. To remove a species,
select it in the list and click the Remove concentration button ( ) under the table.
Edit the names of the species directly in the table.

The species are dependent variables, and their names must be unique with
respect to all other dependent variables in the component.

Domain, Boundary, and Pair Nodes for the Transport of

Concentrated Species Interface
The Transport of Concentrated Species Interface has these 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.

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.

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.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 273

 These nodes are described in this section or as indicated:

• Electrode Surface Coupling • Porous Electrode Coupling1

• Equilibrium Reaction • Reaction
• Flux • Reaction Coefficients1
• Flux Discontinuity • Reaction Sources
• Inflow • Surface Equilibrium Reaction
• Initial Values • Symmetry
• Mass Fraction • Thin Impermeable Barrier1
• No Flux • Turbulent Mixing
• Open Boundary • Transport Properties
• Outflow
• Porous Media Transport Properties

Some features require certain add-on modules. See details https://

www.comsol.com/products/specifications/
1
The node is described for the Transport of Diluted Species interface.

Transport Properties
The Transport Properties is the main node used to model mass transfer in a fluid
mixture with the Transport of Concentrates species interface. The node adds the
equations governing the mass fractions of all present species, and provides inputs for
the transport mechanisms and for the material properties of the fluid mixture.

The settings in this node are dependent on the check boxes selected under Transport
Mechanisms in the Settings window of the Transport of Concentrated Species
interface.

The Turbulent Mixing subnode is available from the context menu as well as from the
Physics toolbar, Attributes menu.

The options available in this feature differs between COMSOL products. (See https:/
/www.comsol.com/products/specifications/).

274 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

MODEL INPUTS
Specify the temperature and pressure to be used in the physics interface. The
temperature model input is used when calculating the density from the ideal gas law,
but also when thermal diffusion is accounted for by supplying thermal diffusion
coefficients. The pressure model input is used in the diffusional driving force in
Equation 6-3 (that is, when a Maxwell–Stefan Diffusion Model is used) and when
calculating the density from the ideal gas law.

Temperature
Select the source of the Temperature field T:

• Select User defined to enter a value or an expression for the temperature (SI unit: K).
This input is always available.
• If required, select a temperature defined by a Heat Transfer interface present in the
model (if any). For example, select Temperature (ht) to use the temperature defined
by the Heat Transfer in Fluids interface with the ht name.

Absolute Pressure
Select the source of the Absolute pressure p:

• Select User defined to enter a value or an expression for the absolute pressure
(SI unit: Pa). This input is always available.
• In addition, select a pressure defined by a Fluid Flow interface present in the model
(if any). For example, select Absolute pressure (spf) to use the pressure defined in a
Laminar Flow interface with spf as the Name.

DENSITY
Define the density of the mixture and the molar masses of the participating species.

Mixture Density
Select a way to define the density from the Mixture density list — Ideal gas or User
defined:

• For Ideal gas, the density is computed from the ideal gas law in the manner of:
pM
 = -----------
Rg T

Here M is the mean molar mass of the mixture and Rg is the universal gas constant.
The absolute pressure, p, and temperature, T, used corresponds to the ones defined
in the Model Inputs section.
• For User defined enter a value or expression for the Mixture density .

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 275

 Molar Mass
Enter a value or expression for the Molar mass Mw for each species. The default value
is 0.032 kg/mol, which is the molar mass of O2 gas.

CONVECTION
Select the source of the Velocity field u:

• Select User defined to enter manually defined values or expressions for the velocity
components. This input is always available.
• Select a velocity field defined by a Fluid Flow interface present in the model (if any).
For example, select Velocity field (spf) to use the velocity field defined by the Fluid
Properties node fp1 in a Single-Phase Flow, Laminar Flow interface with spf as the
Name.

DIFFUSION
Specify the molecular and thermal diffusivities of the present species based on the
selected Diffusion model.

When using a Maxwell–Stefan Diffusion Model or a Mixture-Averaged Diffusion

Model, select the Binary diffusion input type (Table or Matrix) and specify the Maxwell–
Stefan diffusivities in the table or matrix, then enter the Thermal diffusion coefficients
T
Dw .
F
When using a Fick’s Law Diffusion Model, specify the Diffusion coefficient D w and the
T
Thermal diffusion coefficients D w for each of the species.

Maxwell–Stefan Diffusivity Matrix

Using a Maxwell–Stefan Diffusion Model or a Mixture-Averaged Diffusion Model, the
Maxwell–Stefan diffusivity matrix Dik (SI unit: m2/s) can be specified by a table or
matrix. For a simulation involving Q species the Maxwell–Stefan diffusivity matrix is a
Q-by-Q symmetric matrix, where the diagonal components are 1. Enter values for the
upper triangular components, Dij, which describe the interdiffusion between species i
and j. For the table input type, only upper triangular components (Dij) are listed. The
name of species pair consists of species in the first and second column. For the matrix
input type, the numbering of the species corresponds to the order, from top to
bottom, used for all the input fields for species properties (see for example the molar
mass fields in the Density section). The Maxwell–Stefan diffusivity matrix is used to
compute the multicomponent Fick diffusivities as described in Multicomponent
Diffusivities.

276 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Diffusion Coefficient
Using a Fick’s Law Diffusion Model, the diffusion is by default assumed to be isotropic
F
and governed by one Diffusion coefficient D w (SI unit: m2/s) for each species. To allow
for a general representation, it is also possible to use diffusion matrices (diagonal,
symmetric, or anisotropic).

Thermal Diffusion Coefficient

T
To model thermal diffusion, prescribe the Thermal diffusion coefficients D i
(SI unit: kg/(m·s)), by entering one thermal diffusion coefficient for each species in
the corresponding field. In a multicomponent mixture, the sum of the thermal
diffusion coefficients is zero. The default value for all thermal diffusion coefficients
is 0.

Specify the molecular and thermal diffusivities of the present species based on the
selected Diffusion model.

KNUDSEN DIFFUSION
The Knudsen diffusion transport mechanism accounts for the interaction of the species
with the surroundings (interspecies collisions excluded) — for example, the pore wall
when a species passes through porous media.

Depending on which Diffusion model is selected, either the Fick’s law or the
M
Mixture-averaged diffusion coefficient D i is corrected with the Knudsen diffusion
K
coefficient D i in the following way

MK  1 1 -
-1
Di =  --------
M
- + -------
K

 Di Di 

For gases, the Kinetic gas theory is often valid and requires the Mean path length path
(SI unit: m). Typically, for transport in porous media, the pore diameter can be entered
here. For other cases, choose User defined.

MIGRATION IN ELECTRIC FIELD

This section is available when the Migration in electric field check box is selected for the
Transport of Concentrated Species interface.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 277

 Electric Potential
• Select User defined to enter a value or expression for the electric potential. This input
is always available.
• If required, select an electric potential defined by an AC/DC interface that is
present in the model (if any). For example, select Electric potential (ec) to use the
electric field defined by the Current Conservation node cucn1 in an Electric
Currents interface ec.

Settings for the mobilities are used for the Mixture-averaged and Fick’s law transport
models. By default the mobility is set to be calculated based on the species diffusivities
and the temperature using the Nernst-Einstein relation. To manually specify the
mobilities, select User defined for the mobility um,c (SI unit: s·mol/kg) and enter one
value for each species.

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 the Model Inputs section.

Porous Media Transport Properties

The Porous Media Transport Properties node is used to model mass transfer in porous
media using the Transport of Concentrated Species interface. The node adds the
equations governing the mass fractions of all present species, and provides inputs for
the transport mechanisms and for the material properties of the fluid mixture.

The settings in this node are dependent on the check boxes selected under Transport
Mechanisms in the Settings window of the Transport of Concentrated Species
interface.

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

https://www.comsol.com/products/specifications/ for more details on
availability.

MODEL INPUTS
Specify the temperature and pressure to be used in the physics interface. The
temperature model input is used when calculating the density from the ideal gas law,
but also when thermal diffusion is accounted for by supplying thermal diffusion
coefficients. The pressure model input is used in the diffusional driving force in

278 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Equation 6-3 (that is, when a Maxwell–Stefan Diffusion Model is used) and when
calculating the density from the ideal gas law.

Temperature
Select the source of the Temperature field T:

• Select User defined to enter a value or an expression for the temperature (SI unit: K).
This input is always available.
• If required, select a temperature defined by a Heat Transfer interface present in the
model (if any). For example, select Temperature (ht) to use the temperature defined
by the Heat Transfer in Fluids interface with the ht name.

Absolute Pressure
Select the source of the Absolute pressure p:

• Select User defined to enter a value or an expression for the absolute pressure
(SI unit: Pa). This input is always available.
• In addition, select a pressure defined by a Fluid Flow interface present in the model
(if any). For example, select Absolute pressure (spf) to use the pressure defined in a
Laminar Flow interface with spf as the name.

MATRIX PROPERTIES
The default selection for Porosity is From material. In order to use a porosity defined
in a material, specify the material using the Porous material list, and select From material
from the Porosity list.

Select From pellet bed densities to compute the porosity using the (dry bulk) Bed
density b and the (single phase) Pellet density pe (for example, when there is a
reactive pellet bed in the same domain). The porosity is then defined from

b
 p = 1 – --------
 pe

For User defined, enter a value or expression for the Porosity, p (dimensionless), of the
porous media.

DENSITY
Use this section to define the mixture density, and to specify the molar masses of the
participating species.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 279

 Mixture Density
Select a way to define the density from the Mixture density list — Ideal gas or User
defined:

• For Ideal gas, the density is computed from the ideal gas law in the manner of:
pM
 = -----------
Rg T

Here M is the mean molar mass of the mixture and Rg is the universal gas constant.
The absolute pressure, p, and temperature, T, used corresponds to the ones defined
in the Model Inputs section.
• For User defined enter a value or expression for the Mixture density .

Molar Mass
Enter a value or expression for the Molar mass Mw for each species. The default value
is 0.032 kg/mol, which is the molar mass of O2 gas.

CONVECTION
Select the source of the Velocity field u:

• Select User defined to enter values or expressions for the velocity components. This
input is always available.
• Select a velocity field defined by a Fluid Flow interface present in the model (if any).
For example, select Velocity field (spf) to use the velocity field defined by the Fluid
Properties node fp1 in a Single-Phase Flow, Laminar Flow interface with spf as the
Name.

DIFFUSION
Specify the species molecular and thermal diffusivities in nonporous media in the
manner described for the Transport Properties node.

To account for the effect of porosity in the diffusivities, select an Effective diffusivity
model — Millington and Quirk model, Bruggeman model, Tortuosity model, or No
correction. Using one of the first four models, the effective transport factor, fe, is
defined from the porosity and the fluid tortuosity factor in the manner of:

p
f e = ----- (6-6)
F

280 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

For No correction, the effective transport factor is set to one.
–1  3
• For the Millington and Quirk model, the effective transport factor is  F =  p .
–1  2
• For the Bruggeman model, the effective transport factor is  F = p .
• For the Tortuosity model, specify the tortuosity factor is F.

The species diffusivities and mobilities are automatically adjusted for porous media
transport using the effective transport factor.

MIGRATION IN ELECTRIC FIELD

This section is available when the Migration in electric field check box is selected in the
Transport Mechanisms section of the interface, select the source of the Electric
potential V:

• Select User defined to enter a value or expression for the electric potential. This input
is always available.
• If required, select an electric potential defined by an AC/DC interface that is
present in the model (if any). For example, select Electric potential (ec) to use the
electric field defined by the Current Conservation node cucn1 in an Electric
Currents interface ec.

Settings for the mobilities are needed for the Mixture-averaged and Fick’s law diffusion
models. By default the mobility is set to be calculated based on the species diffusivities
(adjusted by the Effective diffusivity model in the Diffusion section) using the
Nernst-Einstein relation. To manually specify the mobilities, select User defined for the
mobility um,w (SI unit: s·mol/kg) and enter one value for each species.

Enter the Charge number zc (dimensionless, but requires a plus or minus sign) for each
species.

The temperature (if you are using mobilities based or the Nernst-Einstein relation) is
taken from the Model Inputs section.

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

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 281

 subnodes. The molar fluxes are multiplied by the species molar masses to obtain the
corresponding mass fluxes.

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

https://www.comsol.com/products/specifications/ for more details on
availability.

MASS TRANSFER TO OTHER PHASES

When using the Reacting Flow coupling feature to model coupled momentum and
mass transport, boundary conditions that results in a nonnegligible mass flux can be
consistently handled by accounting for The Stefan Velocity.

Select Account for Stefan velocity to update the Stefan velocity in accordance with the
mass flux from the electrode reactions. One example that may benefit from this is when
modeling gas diffusion electrodes.

Turbulent Mixing
Use this node to account for the species mixing caused by turbulent flow, typically
when the specified velocity field corresponds to a RANS solution. The node defines
the turbulent mass diffusion from the turbulent kinematic viscosity and a turbulent
Schmidt number.

This node is available if the Diffusion model is Mixture-averaged or Fick’s law.

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

https://www.comsol.com/products/specifications/ for more details on
availability.

The Turbulent Mixing feature should not be used together with the
Reacting Flow coupling feature. In this case the turbulent mixing is added
by the coupling feature.

The Turbulent Mixing subnode can be added from the context menu (right-click the
Transport Properties parent node) or from the Physics toolbar, Attributes menu.

TURBULENT MIXING
Physics interfaces capable of solving for turbulent fluid flow provide the turbulent
kinematic viscosity, and these appear as options in the Turbulent kinematic viscosity T

282 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

(SI unit: m2/s) list. The list always contains the User defined option that makes it
possible to enter any value or expression.

The default Turbulent Schmidt number ScT is 0.71 (dimensionless).

Reaction
Use the Reaction node to specify the reaction kinetics for a single homogeneous
chemical reaction. The resulting mass source terms for the species involved in the
reaction are automatically defined and added on the selected domains. For turbulent
flow, the Reaction node includes the Eddy-dissipation turbulent-reactions model.

REACTION RATE
Select a Reaction rate — Automatic (the default), or User defined. Selecting Automatic
the laminar flow reaction rate is computed using the mass action law

For User defined, input a custom expression or constants for the Reaction rate r.

Specify the reaction stoichiometry by entering values for the stoichiometric coefficients
(dimensionless) of each species. Enter negative values for reactants and positive values
for products.

RATE CONSTANTS
When the Use Arrhenius expressions check box is not selected, input custom expressions
or constants for the Forward rate constant kf and Reverse rate constant kr.

When the Use Arrhenius expressions check box is selected, enter values for the following
parameters of the forward and reverse reactions:

• Forward frequency factor Af and Reverse frequency factor Ar (dimensionless)

• Forward activation energy Ef and Reverse activation energy Er
• Forward temperature exponent nf and Reverse temperature exponent nr
(dimensionless)

TURBULENT FLOW
Note this section is only available when then licensed to the CFD Module (see https:/
/www.comsol.com/products/specifications/).

When the Turbulent-reaction model is set to None, laminar flow is assumed and the
reaction source terms are defined from the reaction stoichiometry and reaction rates
prescribed.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 283

 When the Turbulent-reaction model is set to Eddy-dissipation, turbulent flow will be
accounted for in the reaction mass sources. In this case, enter values for the Turbulent
reaction model parameters ED and  ED (dimensionless).

The Eddy-dissipation model also requires an estimation of the turbulent mixing time of
the fluid flow turbulence. When a Fluid Flow interface defining it is present in the
model, it can be selected from the Turbulence time scale list. For example, select
Turbulence time scale (spf/fp1) to use the time scale defined by the Fluid Properties node
fp1 in a Turbulent Flow, k- interface with the Name set to spf.

REGULARIZATION
Select Rate expression in order to regularize the individual rate expressions that are
added to each species. If the mass fraction for a reactant species i becomes smaller
than its damping limit, idl, the rate expression added to species i is reduced linearly.
If i  0 for a reactant species, the reaction rate contribution to that species is
completely removed. Similarly, the if the mass fraction for a product species j becomes
larger than 1  jdl, the rate expression added to that species is damped linearly. If j 
1 for a product species, the reaction rate contribution to that species is completely
removed.

The default value for the damping limit, idl, is 106, which is appropriate for most
applications, but can require adjustment when working with for example catalytic trace
species.

Regularization of the rate expressions adds considerable stability to the reaction

expressions, but should optimally only be used as a mean to reach convergence. If the
regularization is active in too large parts of the domain, the mass balance can become
affected since the regularization acts on the contributions to each individual species,
not the reaction as a whole.

Reaction Sources
Use the Reaction Sources node to define mass source terms from one or more chemical
reactions. Both homogeneous reactions as well as heterogeneous reactions occurring
in a porous media can be studied. The node also includes the possibility to pick up
automatically defined source term definitions from a Chemistry physics interface.

284 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

REACTIONS
Add an expression for the reaction mass source, Ri, for each individual species present,
except for the one computed from the mass constraint (see Species). Enter a value or
expression in the field for the corresponding species.

Select the Mass transport to other phases check box if mass is leaving or entering the
fluid as a result of the reactions, for instance due to condensation or vaporization in a
porous matrix. In this case the mass source for the species calculated from the mass
constraint can also be specified. The net mass transfer corresponds to the sum of the
mass sources for all species.

REACTING VOLUME
When specifying reaction sources for a species in porous media, the specified mass
source may have the basis of the total volume, or the pore volume. For nonporous
domains, the Reacting Volume setting has no impact.

• For Total volume, the reaction mass source expressions are specified per unit volume
of the model domain.
• For Pore volume, the reaction mass source expressions are specified per unit volume
pore space. In this case the reaction mass sources will be multiplied by the domain
porosity p (p equals unity for nonporous domains).

Initial Values
The Initial Values node adds initial values for the mass fractions that can serve as an
initial condition for a transient simulation, or as an initial guess for a nonlinear solver.
If required, add additional Initial Values nodes from the Physics toolbar.

INITIAL VALUES
The initial mass fractions can be specified using a number of quantities. Select the type
of input from the Mixture specification list. Select:

• Mass fractions (the default) to enter mass fractions (01 for example)
• Mole fractions to enter mole fractions (x01 for example)
• Molar concentrations (SI unit: mol/m3) to enter molar concentrations (c01 for
example)
• Number densities (SI unit: 1/m3) to enter number densities (n01 for example)
• Densities (SI unit: kg/m3) to enter densities (01 for example)

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 285

 Enter a value or expression in the field for each species except for the one computed
from the mass constraint.

INITIAL MIXTURE DENSITY

When the selecting Molar concentrations, Number densities, or Densities are selected
from the Mixture specification list, the should also be specified. Select Ideal gas or User
defined from the Initial mixture density list.

• For Ideal gas, also specify the Initial pressure p0 and the Initial Temperature T0. Note
that dependent variables solved for are evaluated to zero for initial values. When
solving for pressure or temperature together with the mass fractions, apply the initial
values from the corresponding interfaces here as well.
• For User defined, input a custom for the Initial mixture density m0.

Mass Fraction
The Mass Fraction node adds boundary conditions for the species mass fractions. For
example, the following condition specifies the mass fraction of species i: i = i,0.

Set the mass fractions of all species except the one computed from the mass constraint.
This ensures that the sum of the mass fractions is equal to one (see Species). This node
is available for exterior and interior boundaries.

MASS FRACTION
Specify the mass fraction for each species individually. Select the check box for the
species to specify the mass fraction, and 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 mass fraction of that species.

MASS TRANSFER TO OTHER PHASES

When using the Reacting Flow coupling feature to model coupled momentum and
mass transport, boundary conditions that results in a nonnegligible mass flux can be
consistently handled by accounting for The Stefan Velocity.

Select Account for Stefan velocity to update the Stefan velocity in accordance with the
prescribed mass fractions. Examples of cases that may benefit from this are, for
example, when modeling surface reactions or phase change on an exterior boundary.

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

286 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Flux
The Flux node is available on exterior boundaries and can be used to specify the mass
flux. The boundary mass flux for each species is defined in the manner of

– n  j i = j 0 i (6-7)

where n denotes the outward pointing normal of the boundary. The prescribed flux
j0,i can contain an arbitrary flux expression. It can for example be used to represent a
heterogeneous reaction or a separation process occurring at the boundary. The flux can
for example be a function of i, the temperature, the pressure or even the electric
potential.

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, for example due to a fluid
injection, it is often convenient to prescribe the total flux including convection. To do
so select Include in the Convection section. In this case the prescribed flux is defined as:

– n   j i + u i  = J 0

MASS TRANSFER TO OTHER PHASES

When using the Reacting Flow coupling feature to model coupled momentum and
mass transport, boundary conditions that results in a nonnegligible mass flux can be
consistently handled by accounting for The Stefan Velocity.

Select Account for Stefan velocity to update the Stefan velocity in accordance with the
prescribed flux. Examples of cases that benefit from this are for example when
modeling surface reactions or phase change on an exterior boundary. The Stefan
velocity represents the mixture velocity resulting from mass fluxes at the wall. This
section is not available when Include is selected in the Convection section.

INWARD FLUX
Specify the Inward flux for each species individually. Select the check box for the species
to prescribe a flux for and 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 flux of that species. Use a positive value for an inward flux.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 287

 External convection
Set Flux type to External convection to prescribe a mass 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

j 0 i = k  i   b i –  i  (6-8)

where ki is a mass transfer coefficient and b,i is the bulk mass fraction, the typical
mass fraction far into the surrounding exterior domain.

Inflow
The Inflow node adds a boundary condition for an inflow boundary, defining the
composition of the mixture. The node is available for exterior boundaries. The mixture
composition can be specified using the following quantities:

• Mass fractions: i  0,i

• The mole fraction: xi  x0,i
• The molar concentration: ci  c0,i
• The number density, which describes the number of particles per volume: ni  n0,i
• The density: i  0,i
• The mass flow rates.

The node requires input for all species. (The Mass Fraction node can be used to specify
boundary mass fractions for a subset of the active species in the interface.)

INFLOW
Select a Mixture specification:

• Mass fractions (the default) to enter mass fractions (01, for example)
• Mole fractions to enter mole fractions (x01 for example)
• Molar concentrations (SI unit: mol/m3) to enter molar concentrations (c01, for
example)
• Number densities (SI unit: 1/m3) to enter number densities (n01, for example)
• Densities (SI unit: kg/m3) to enter densities (01, for example)
• Mass flow rates (SI unit: kg/s) to enter the total mass flow over the boundary
(Jin1, for example)

288 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Enter a value or expression in the field for each species except for the one computed
from the mass constraint.

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

No Flux
The No Flux node is the default boundary condition available for exterior boundaries.
It should be used on boundaries across which there is no mass flux, typically exterior
solid walls where no surface reactions occur. The condition applied for each species
corresponds to

–n  ji = 0

where n denotes the outward pointing normal of the boundary.

Outflow
The Outflow node is the preferred boundary condition at outlets where the species are
to be transported out of the model domain. It is useful, for example, in mass transport
models where it is assumed that convection is the dominating effect driving the mass
flow through the outflow boundary. This node is available for exterior boundaries. The
boundary condition is applied to all species and corresponds to one of the following
equations depending on the selected diffusion model:

• For the Mixture-Averaged Diffusion Model:

m
– n  D i  i = 0

• For the Fick’s Law Diffusion Model:

f
– n  D i  i = 0

Symmetry
The Symmetry node can be used to represent boundaries where the species
concentration is symmetric; that is, there is no mass flux in the normal direction across
the boundary:

– n  N = – n    i u + j i  = 0

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 289

 This boundary condition is identical to the No Flux node, but applies to all species and
cannot be applied to individual species. The Symmetry node is available for exterior
boundaries.

Flux Discontinuity
The Flux Discontinuity node represents a discontinuity in the mass flux across an interior
boundary:

–n   Nd – Nu  = N0 N =   i u + j i 

where the value of N0 specifies the size of the flux jump evaluated from the down to
the upside of the boundary.

FLUX DISCONTINUITY
Specify the jump in species mass flux. Use a positive value for increasing flux when
going from the downside to the upside of the boundary. The boundary normal points
in the direction from the downside to the upside of an interior boundary and can be
plotted for visualization.

Select the Species check boxes to specify a flux discontinuity, and enter a value or
expression for the Flux discontinuity N0 (SI unit: kg/(m2·s)) in the corresponding field,
N0, w1 for example. To use a different boundary condition for a specific species, click
to clear the check box for the flux discontinuity of that species.

Open Boundary
Use the Open Boundary node to set up mass transport across boundaries where both
convective inflow and outflow can occur. Use the node to specify an exterior species
composition on parts of the boundary where fluid flows into the domain. A condition
equivalent to the Outflow node applies to the parts of the boundary where fluid flows
out of the domain. The direction of the flow across the boundary is typically calculated
by a Fluid Flow interface and is entered as Model Inputs.

EXTERIOR COMPOSITION
Enter a value or expression for the species composition. Select:

• Mass fractions (the default) to enter mass fractions (0,1, for example)
• Mole fractions to enter mole fractions (x0,1, for example)

290 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

• Molar concentrations (SI unit: mol/m3) to enter molar concentrations (c0,1, for
example)
• Number densities (SI unit: 1/m3) to enter number densities (n0,1, for example)
and to describe the number of particles per volume n  n0
• Densities (SI unit: kg/m3) to enter densities (0,1, for example)

A concentration quantity other than the mass fractions can only be used
when all species are defined.

Equilibrium Reaction
Use this node to model a reaction where the kinetics is assumed 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.

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

https://www.comsol.com/products/specifications/ for more details on
availability.

EQUILIBRIUM CONDITION
Selecting Equilibrium constant in the list, the following equilibrium condition based on
the species activities and the law of mass action is used


 ai i
i  products
K eq = ----------------------------------
–
 ai i
i  reactants

where i are the stoichiometric coefficients and the species activities are defined from
the concentration, ci, and the unit activity concentration ca0.

ci
a i = -------
c a0

Enter a value or expression for the dimensionless Equilibrium constant Keq, and the Unit
activity concentration Ca0.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 291

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

STOICHIOMETRIC COEFFICIENTS
Enter a value for the stoichiometric coefficient for all participating species. 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.

Surface Equilibrium Reaction

Use this node to model an equilibrium reaction on a boundary (surface). The kinetics
of the reaction is assumed so fast that the equilibrium condition is fulfilled at all times.
The node solves for an additional degree of freedom (the mass flux Jeq) to fulfill the
equilibrium condition at all times in all space coordinates along the boundary.

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

https://www.comsol.com/products/specifications/ for more details on
availability.

The settings for this node are the same as for Equilibrium Reaction except for the
setting in the section below.

MASS TRANSFER TO OTHER PHASES

When using the Reacting Flow coupling feature to model coupled momentum and
mass transport, boundary conditions that results in a nonnegligible mass flux can be
consistently handled by accounting for The Stefan Velocity. Select Account for Stefan
velocity to update the Stefan velocity in accordance with the prescribed mass fractions.
Examples of cases that may benefit from this are for example when modeling surface
reactions or phase change on an exterior boundary.

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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 | 293

 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
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 species 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

Species Concentration Input Table

Use the Species concentration input table to specify the concentrations to be used as
arguments in variables generated by the Reaction and the Species features (the reaction
rate for example). The species concentrations are also used in the mixture properties
(transport and thermodynamic properties).

When Diluted species is selected in the Type list in the Mixture Properties section, enter
the names of the dependent variables in the Molar concentration column. When
Concentrated species is selected, enter the names of the dependent variables in the Mass
fraction column.

294 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Surface Species
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
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
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.

Thermodynamics Coupling
When coupled to Thermodynamics is enabled, the species in the Chemistry interface
can be matched 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
interface to a species in the coupled thermodynamic system. For each species matched,
the required property parameters and functions are added under the corresponding
thermodynamic system. When all species are matched, the interface is considered fully
coupled and functions representing mixture properties, such as the density, are also
added automatically under the corresponding thermodynamic system.

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.

THE CHEMISTRY INTERFACE | 295

 CALCULATE TRANSPORT PROPERTIES
Select the Calculate mixture properties check box 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 fits the model or if User defined expressions are more suitable. In general,
the Chemistry interface calculates properties in the same way as the Reaction
Engineering interface.

Transport Properties

ACTIVITY
Select the Use activity check box to solve for species activities instead of species
concentrations, which is a common approach when non-ideal fluids are modeled.

An activity coefficient other than 1 can be set for each species for the Species node in
the Species Concentration/Activity section.

CHEMKIN IMPORT FOR SPECIES PROPERTIES

®
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.

EXTRA DIMENSION
Select Define variables in extra dimension when the current Chemistry interface is
coupled to a feature on an extra dimension. An example of this is when the
concentrations in the Concentration input column of the Model Inputs, Concentration
correspond to pellet concentrations from a Transport of Diluted Species interface’s
Reactive Pellet Bed feature (available with the Chemical Reaction Engineering
Module).

When selected, generated variables will be defined using concentrations averaged over
the extra dimension. Note that the generated variables are global in order be available

296 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

on the main geometry, in contrast to variables on the extra dimension which only exist
on the corresponding dimension.

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
1
• Reaction Thermodynamics • 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 e.g. 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.

THE CHEMISTRY INTERFACE | 297

 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 =  ij rj (6-9)
j

where ij 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:

–  ij

f
rj = kj ci (6-10)
i  react

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

–  ij 
 
f r
rj = kj ci – kj c i ij (6-11)
i  react i  prod

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

298 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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: (m/mol)  1/s, where  equals the order with respect to
volumetric specfies. When surface species are present — identified by their “(ads)”
suffix — the unit is instead given by m  2/mol/s, where 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 6-1: The reaction order can be manually specified for a user defined reaction rate.

THE CHEMISTRY INTERFACE | 299

 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 6-10).

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)

300 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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:


 c i ij
i  prod
K eqj = ---------------------------
–
 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.

THE CHEMISTRY INTERFACE | 301

 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 =   ij h i –   –  ij h i (6-12)
i  prod i  react

Entropy of Reaction
The Entropy of reaction S (SI unit: J/(mol·K)) comes from a similar expression:

Sj =   ij s i –   –  ij s i (6-13)
i  prod i  react

In Equation 6-12 and Equation 6-13, 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, ij, are defined as being negative for reactants and
positive for products. Using Equation 6-12 and Equation 6-13 to equate the Gibbs
free energy of reaction enables the equilibrium constant to be expressed according to
Equation 6-12.

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.

302 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

It is also possible to add and define an individual Species node: on the Chemistry toolbar
click Species or right-click the Chemistry node and select it from the context menu.

SPECIES NAME
When a Species node is automatically generated using the Formula text field for the
Reaction node, the Species name is also automatically generated.

For a Species node added individually, enter a Species name in the field and click Apply.

Creating Valid Species Names and Labeling

SPECIES TYPE
Select a species type — Bulk species, Surface species, or Solvent.

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

THE CHEMISTRY INTERFACE | 303

 It is possible to specify the species density  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 in the reactor since the reaction of the species can depend both
on bulk reaction R and surface reaction Rads rates. For a surface species, only the
surface reaction rate Rads appears.

ADDITIONAL SOURCE
The Additional Source section is available in order to include additional rate
contribution for the species to the reaction kinetics. When the Additional source check
box is selected, add an Additional rate expression in the text field (SI unit: mol/m3).

SPECIES CONCENTRATION/ACTIVITY
To account for non-ideality in the fluid mixture, adjust the activity coefficient in the
Activity coefficient input field. This input field is only shown if activity instead of
concentration has been chosen in the interface, that is, the Use activities 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.

304 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

THE CHEMISTRY INTERFACE | 305

 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.

306 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

r H
E therm = – ----------- (6-14)
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.

THE CHEMISTRY INTERFACE | 307

 For the case when reaction kinetics data are entered manually into the Reaction table
and temperature dependent reaction kinetics apply (Feature Nodes Available for the
Chemistry Interface check box is selected), right-click to add a Reaction
Thermodynamics subnode or select it from the Chemistry toolbar, Attributes menu. In
it, the Enthalpy of Reaction (J/mol) for each reaction can be specified.

REACTION TABLE
The reversible reactions in the Reaction table are numbered and contain reactants,
products, and kinetic parameters describing the reaction. Use the buttons under the
Reaction table to add and sort the reaction details.

• In general, use the Move Up ( ), Move Down ( ), and Delete ( ) buttons and
the fields under tables to edit the table contents. Or right-click a table cell and select
Move Up, Move Down, or Delete.
• The Add button ( ) adds default reactant, A, and product, B, with a default. Click
the corresponding field to edit the reactant, product, or parameters. After editing
the Species Group node is also updated. It is created together with the reaction
group.
• You can save the parameters to a text file to reuse in other models. Click the Save to
File button ( ) and enter a File name in the Save to File dialog box, including the
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.

In the case of twenty or more reactions the Disable updating variables during editing
table check box is available. Select this to speed up editing text fields; automatic
updates related to edits do not occur until you click to clear the check box.

308 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

CREATE REACTION AND SPECIES
Enter a reaction number in the Moving reaction (with the number) from table text field
and click Create Reaction to remove the reaction from the Reaction table to the model
tree. This introduces a reaction node named after the reaction number and species
names and simultaneously creates corresponding species nodes. This action is
powerful, since it enables all the editing possibilities available for Reaction and Species
nodes.

Equilibrium Reaction Group

The Equilibrium Reaction Group node ( ) allows for input of a large number of
equilibrium reactions in the same table. This node functions in the same way as the
Reversible Reaction Group for reversible reactions.

Add the node from the Chemistry toolbar or right-click Chemistry and add it from the
context menu.

For the case when reaction kinetics data are entered manually into the Reaction table
and temperature dependent reaction kinetics apply (Feature Nodes Available for the
Chemistry Interface check box is selected), right-click to add a Reaction
Thermodynamics subnode or select it from the Chemistry toolbar, Attributes menu. In
it, the Enthalpy of Reaction (J/mol) for each reaction can be specified.

REACTION TABLE
The equilibrium reactions in the Reaction table are numbered and contain reactants,
products, and kinetic parameters describing the reaction. Use the buttons under the
Reaction table to add and sort the reaction details.

• In general, use the Move Up ( ), Move Down ( ), and Delete ( ) buttons and
the fields under tables to edit the table contents. Or right-click a table cell and select
Move Up, Move Down, or Delete.
• The Add button ( ) adds default reactant, A, and product, B, with a default. Click
the corresponding field to edit the reactant, product, or parameters. After editing
the Species Group node is also updated. It is created together with the reaction
group.
• You can save the parameters to a text file to reuse in other models. Click the Save to
File button ( ) and enter a File name in the Save to File dialog box, including the
extension .txt. Click Save to store the parameters in a text file or in a Microsoft
Excel Workbook spreadsheet if the license includes LiveLink™ for Excel®. The
information is saved in space-separated columns in the same order as displayed on

THE CHEMISTRY INTERFACE | 309

 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.

In the case of twenty or more reactions the Disable updating variables during editing
table check box is available. Select this to speed up editing text fields; automatic
updates related to edits do not occur until you click to clear the check box.

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 also automatically added when either the Reversible Reaction Group or
the Equilibrium Reaction Group are used.

For the case of temperature dependent reaction kinetics (Feature Nodes Available for
the Chemistry Interface check box is selected), a Species Thermodynamics subnode is
automatically created in which the thermodynamic properties of the species can be
specified.

Reaction Thermodynamics
The Reaction Thermodynamics subnode ( ), the Enthalpy of Reaction (J/mol) of
each reaction can be specified. This node overrides all the automatically calculated
reaction enthalpies as defined in the Species Thermodynamics subnode.

Add the Reaction Thermodynamics node from the Chemistry toolbar, Attributes menu.
Alternatively, when the Feature Nodes Available for the Chemistry Interface check box
is selected on the Chemistry interface Settings window, right-click a Reversible

310 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

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 when the Feature Nodes Available
for the Chemistry Interface check box is selected on the Chemistry interface Settings
window.

THE CHEMISTRY INTERFACE | 311

 T he N e r ns t - P l an c k- Poi sson E q u at i on s
Interface
The Nernst-Planck-Poisson Equations interface ( ), found under the Chemical Species
Transport branch ( ) when adding a physics interface, is a predefined multiphysics
interface for modeling transport of electrolyte species without the otherwise common
assumption of local electroneutrality. This allows for simulating charge separation that
typically arises close to an electrode surface, where ions in the electrolyte are attracted
and repelled by unscreened excess charge on the electrode. The charge separation
region, also called the diffuse double layer, normally extends a few nanometers away
from the electrode surface into the electrolyte. The study of the charge separation is
important to applications that consider very thin layers of electrolyte, such as
electrochemical capacitors, atmospheric corrosion problems, ion-selective field effect
transistors (ISFETs), and nanoelectrochemistry.

The Nernst–Planck–Poisson Equations predefined multiphysics interface adds ( )

(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 ( ) 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.

312 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Finally, a ( ) 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

Fuel_Cell_and_Electrolyzer_Module/General_Electrochemistry/
diffuse_double_layer

THE NERNST-PLANCK-POISSON EQUATIONS INTERFACE | 313

 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.

314 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

THE ELECTROPHORETIC TRANSPORT INTERFACE | 315

 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.

316 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Also the Apply smoothing to boundary fluxes check box is available if the previous check
box is checked. The smoothing can provide a more well-behaved flux value close to
singularities.

For details about the boundary fluxes settings, see Computing Accurate Fluxes in the
COMSOL Multiphysics Reference Manual.

Regarding the Value type when using splitting of complex variables, see Splitting
Complex-Valued Variables in the COMSOL Multiphysics Reference Manual.

DEPENDENT VARIABLES
The dependent variable name for the electrolyte potential variable is phil by default.

The name of the concentration dependent variables are named as el.xxx, where the el is
the name of the interface as set above, and the xxx string is controlled by the Species
name setting on the individual species nodes.

FURTHER READING

• Theory for the Electrophoretic Transport Interface

• Numerical Stabilization in the COMSOL Multiphysics Reference
Manual.
• In the COMSOL Multiphysics Reference Manual, see Table 2-4 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

THE ELECTROPHORETIC TRANSPORT INTERFACE | 317

 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.

318 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 319

 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.

320 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 321

 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 .

322 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 323

 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,  l, to be equal to the Boundary
electrolyte potential,  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.

324 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 325

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

n   – D c  = 0

326 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

THE SURFACE REACTIONS INTERFACE | 327

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

328 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

These nodes are described in this section:

• Initial Values
• 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 s (SI unit: mol/m2). The default
is 2 x 10-5 mol/m2.

Enter a Site occupancy number i (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.

THE SURFACE REACTIONS INTERFACE | 329

 This section is only present if the number of surface species is 1 or higher.

BULK SPECIES
For each bulk species enter the Molar mass Mi (SI unit: kg/mol) and the Density i
(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.

330 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

THE SURFACE REACTIONS INTERFACE | 331

 The Reacting Flow Interfaces
The Fuel Cell & Electrolyzer Module includes predefined multiphysics interfaces that
couple fluid with mass transport and reactions.

Selecting any of these interfaces under the Chemical Species Transport>Reacting Flow or
Chemical Species Transport>Reacting Flow in Porous Media branches of the Model Wizard
or Add Physics windows, adds a fluid flow interface and either a Transport of Diluted
Species or Transport of Concentrated Species interface to the Model Builder.

In addition, the Multiphysics node Reacting Flow is added. The Reacting Flow node
predefines and controls the couplings between the mass and fluid transport in order to
facilitate easy set up of models.

In this section:

• The Reacting Laminar Flow Interface

• The Reacting Flow Coupling Feature
• Physics Interface Features

The Reacting Laminar Flow Interface

The Reacting Laminar Flow multiphysics interface is used to simulate laminar flow
coupled to species transport in a gas or liquid.

It combines the Laminar Flow, and Transport of Concentrated Species interfaces. The
Reacting Flow multiphysics coupling, which is added automatically, couples fluid flow
and mass transport. The fluid flow can either be free flow or flow in a porous medium.
The species transport supports both a mixture, where the concentrations are of
comparable order of magnitude, and low-concentration solutes in a solvent.

The interface can be used for stationary and time-dependent analysis in 2D, 2D axial
symmetry, and 3D.

On the constituent physics interfaces:

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. A
Fluid Properties feature is active by default on the entire interface selection. A Fluid and
Matrix Properties feature can be added in order to model flow in porous media by
solving the Brinkman equations.

332 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

The Transport of Concentrated Species interface solves for an arbitrary number of mass
fractions. The species equations include transport by convection, diffusion and,
optionally, migration in an electric field.

The Reacting Laminar Flow interface triggers pseudo time stepping for the
flow equations when Use pseudo time stepping for stationary equation form
in the Fluid Flow interface is set to Automatic from physics.

The Reacting Flow Coupling Feature

Use the Reacting Flow ( ) multiphysics coupling to simulate mass transport and
reactions in a gas or liquid mixture where the fluid flow can be dependent on the
mixture composition.

DOMAIN LEVEL SYNCHRONIZATION

The Reacting Flow coupling synchronizes the features from a Single-Phase Flow, or
Brinkman Equations, interface and a Transport of Concentrated Species interface.
When added, the density in the Single-Phase Flow interface is automatically
synchronized to the one defined by the Transport of Concentrated Species interface.
Conversely, the velocity field used by the latter interface is synchronized to the one
computed in the former interface.

THE STEFAN VELOCITY

The Reacting Flow coupling feature automatically couples mass transfer on boundaries
and applies a corresponding velocity contribution for the flow. Prescribing a net mass
boundary flux in the Transport of Concentrated Species interface, either using a Flux or
Mass Fraction feature, the Reacting Flow feature computes The Stefan Velocity and
applies this in Wall features using the same selection.

MASS TRANSFER TO OTHER PHASES IN POROUS MEDIA

When coupled to the Brinkman Equations interface, the Reacting Flow node
automatically computes the net mass source or sink in a Reactions (when Mass transfer
to other phases is enabled) node in the Transport of Concentrated Species interface and
adds the corresponding source/sink to the momentum equations of the Fluid and
Matrix Properties domains.

SETTINGS
The Label is the default multiphysics coupling feature name.

THE REACTING FLOW INTERFACES | 333

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

The default Name (for the first multiphysics coupling feature in the model) is rf1.

DOMAIN SELECTION
The Reacting Flow coupling is automatically defined on the intersection of the
selections for the coupled interfaces.

The Selection list displays the domains where the coupling feature is active.

COUPLED INTERFACES
This section defines the physics involved in the multiphysics coupling. The Fluid flow
and Species transport lists include all applicable physics interfaces.

The default values depend on how this coupling node is created.

• If it is added from the Physics ribbon (Windows users), Physics contextual toolbar
(Mac and Linux users), or context menu (all users), then the first physics interface
of each type in the component is selected as the default.
• If it is added automatically when a multiphysics interface is chosen in the Model
Wizard or Add Physics window, then the two participating physics interfaces are
selected.

You can also select None from either list to uncouple the node from a physics interface.
If the physics interface is removed from the Model Builder, for example Laminar Flow is
deleted, then the Species transport list defaults to None as there is nothing to couple to.

Click the Go to Source buttons ( ) to move to the main physics interface node for
the selected physics interface.

Click the Show or Hide Physics Properties Settings button ( ) to toggle the display of
physics properties settings affecting the coupling feature. When a turbulence model is
used, turbulent mass transfer is automatically accounted for (see the settings in the
Turbulence section below). Using Reacting Flow, the mass transfer treatment at walls
follows that applied for the fluid flow. Therefore the Wall treatment setting is also
displayed when using a turbulence model. For more information on turbulent mass

334 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

transfer at walls, see the section Mass Transport Wall Functions in the CFD Module
User’s Guide.

If a physics interface is deleted and then added to the model again, then
in order to reestablish the coupling, you need to choose the physics
interface again from the Fluid flow or Species transport lists. This is
applicable to all multiphysics coupling nodes that would normally default
to the once present interface. See Multiphysics Modeling Workflow in the
COMSOL Multiphysics Reference Manual.

TURBULENCE
When the fluid flow interface uses a turbulence model, select an option from the Mass
transport turbulence model list — Kays-Crawford, High Schmidt Number, or User-defined
turbulent Schmidt number.

For User-defined turbulent Schmidt number, enter a Turbulent Schmidt number ScT
(dimensionless).

The turbulent mass transfer added to the mass fraction equations is defined as

T
N i T = – ---------  i
Sc T

where T is the turbulent viscosity defined by the flow interface, and the turbulent
Schmidt number, ScT, depends on the Mass transport turbulence model used.

Note, since the Reacting Flow coupling feature adds the turbulent mass transport, it
should not be combined with a Turbulent Mixing feature (subfeature to Transport
Properties in the Transport of Concentrated Species interface).

Physics Interface Features

Physics 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).

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

operating system you are using.

THE REACTING FLOW INTERFACES | 335

 LAMINAR FLOW
The available physics features for The Laminar Flow interface are listed in the section
Domain, Boundary, Pair, and Point Nodes for Single-Phase Flow in the COMSOL
Multiphysics Reference Manual.

TRANSPORT OF CONCENTRATED SPECIES

The available physics features for The Transport of Concentrated Species interface are
listed in the section .

336 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

The Reacting Flow in Porous Media
Interfaces
The Fuel Cell & Electrolyzer Module includes two predefined multiphysics interface
that couples fluid flow in porous media with mass transport and reactions in porous
media.

Selecting a multiphysics interface under the Chemical Species Transport>Reacting Flow

in Porous Media branch of the Model Wizard or Add Physics windows, a Brinkman
Equations interface combined with either the Transport of Diluted Species in Porous
Media interface or the Transport of Concentrated Species interfaces are added to the
Model Builder.

In addition, the Multiphysics node is added, which includes the multiphysics coupling
feature. The multiphysics coupling feature controls the coupling between the separate
interfaces in order to facilitate easy setup of models.

In this section:

• The Reacting Flow in Porous Media, Transport of Diluted Species Interface

• The Reacting Flow in Porous Media, Transport of Concentrated Species Interface
• The Reacting Flow, Diluted Species Coupling Feature
• The Reacting Flow Coupling Feature
• Physics Interface Features

The Reacting Flow in Porous Media, Transport of Diluted Species

Interface
The Reacting Flow in Porous Media, Transport of Diluted Species interface ( ) is used
to study the flow and chemical composition of a gas or liquid moving through the
interstices of a porous medium.

It combines the Brinkman Equations, and Transport of Diluted Species in Porous Media
interfaces. The Reacting Flow, Diluted Species multiphysics coupling feature, which is
added automatically, couples the fluid flow and mass transport.

The interface can be used for stationary and time-dependent analysis in 2D, 2Daxi and
3D.

THE REACTING FLOW IN POROUS MEDIA INTERFACES | 337

 On the constituent physics interfaces:

The Brinkman Equations interface computes the fluid velocity and pressure fields of
single-phase flow in porous media in the laminar flow regime. A Fluid and Matrix
Properties feature is active by default on the entire interface selection.

The Transport of Diluted Species in Porous Media interface computes the species
concentration in free and porous media, assuming that the species are of solutes,
dissolved in a solvent of significantly higher concentration. The species equations
include transport by convection, diffusion and, optionally, migration in an electric
field.

The Reacting Flow in Porous Media, Transport of Concentrated

Species Interface
The Reacting Flow in Porous Media, Transport of Concentrated Species interface ( ) is
used to study the flow and chemical composition of a gas or liquid moving through
the interstices of a porous medium. The fluid can consist of a mixture of species where
the individual concentrations are of comparable order of magnitude.

It combines the Brinkman Equations, and Transport of Concentrated Species interfaces.

The Reacting Flow multiphysics coupling feature, which is added automatically, couples
the fluid flow and mass transport.

The interface can be used for stationary and time-dependent analysis in 2D, 2Daxi and
3D.

On the constituent physics interfaces:

The Brinkman Equations interface computes the fluid velocity and pressure fields of
single-phase flow in porous media in the laminar flow regime. A Fluid and Matrix
Properties feature is active by default on the entire interface selection.

The Transport of Concentrated Species interface solves for an arbitrary number of mass
fractions in free and porous media. In the current multiphysics interface a Porous Media
Transport Properties feature is active by default on the entire interface selection.

The Reacting Flow, Diluted Species Coupling Feature

For the settings of this feature see The Reacting Flow, Diluted Species Coupling
Feature in the COMSOL Multiphysics Reference Manual.

338 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

The Reacting Flow Coupling Feature
For the settings of this feature see The Reacting Flow Coupling Feature.

Physics Interface Features

Physics 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).

BRINKMAN EQUATIONS
The available physics features for The Brinkman Equations interface are listed in the
Domain, Boundary, Point, and Pair Nodes for the Brinkman Equations Interface
section in the CFD Module User’s Guide.

TRANSPORT OF DILUTED SPECIES

The available physics features for The Transport of Diluted Species interface are listed
in the section.

TRANSPORT OF CONCENTRATED SPECIES

The available physics features for The Transport of Concentrated Species interface are
listed in the section.

THE REACTING FLOW IN POROUS MEDIA INTERFACES | 339

 Theory for the Transport of Diluted
Species Interface
provides a predefined modeling environment for studying the evolution of chemical
species transported by diffusion and convection. 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 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 https://www.comsol.com/products/specifications/

340 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

The section also includes the theory for :

• 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 (6-15)
t

Equation 6-15 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 (6-16)

An input field for the diffusion coefficient is available.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 341

 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 6-15 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 6-15), 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,

i (dimensionless), of the reaction; the species activities of the reacting species
ai (dimensionless); and an equilibrium constant, Keq (1) according to:


 ai i
i  products
K eq = ----------------------------------
–
 ai i
i  reactants

where the species activities are defined as

ci
a i =  c i -------
c a0

where ca0 (SI unit: mol/m3) is the standard molarity, and c,i (dimensionless) an
activity coefficient.

342 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

i
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.

c,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.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 343

 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 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 6-15.

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 (6-17)
t

c
conservative: ----- +    cu  =   J i + R (6-18)
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.

344 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Solving a Diffusion Equation Only
Remove the convection term from Equation 6-17 and Equation 6-18 by clearing the
Convection check box in the Transport Mechanisms section for . 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
https://www.comsol.com/products/specifications/

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

POINT SOURCE
ꞏ
A point source is theoretically formed by assuming a mass injection/ejection, Q c (SI
3
unit: mol/(m ·s)), in a small volume V and then letting the size of the volume tend
to zero while keeping the total mass flux constant. Given a point source strength, qꞏ p,c
(SI unit: mol/s), this can be expressed as

ꞏ ꞏ
lim
V  0  Qc = qp,c (6-19)
V

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

qꞏ p,c test  c 
ꞏ
is added at a point in the geometry. As can be seen from Equation 6-19, Q c must tend
to plus or minus infinity as V tends to zero. This means that in theory the
concentration also tends to plus or minus infinity.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 345

 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 6-19 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
ꞏ
A line source can theoretically be formed by assuming a source of strength Q l,c (SI
3
unit: mol/(m ·s)), located within a tube with cross section S and then letting S tend
to zero while keeping the total mass flux per unit length constant. Given a line source
strength, qꞏ l,c (SI unit: mol/(m·s)), this can be expressed as

ꞏ ꞏ
lim
S  0  Ql,c = ql,c (6-20)
S

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

qꞏ 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.

346 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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
https://www.comsol.com/products/specifications/

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 (6-21)
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.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 347

 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

348 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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:

 –zj um j F cj 
2
i = F (6-22)
j

Equation 6-22 is simply Ohm’s law for ionic current transport and can be simplified to

i = –   (6-23)

where  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 6-23, yields:

   –    = 0 (6-24)

Equation 6-24 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.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 349

 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  (6-25)

350 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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:

  
 c  +   c P i  + ( g c G i) + u  c i =
t l i t t (6-26)
    D D i + D e i  c i  + R i + S i

On the left-hand side of Equation 6-26, 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 6-26 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 p, the liquid volume fraction l; the dry bulk density,  = (1  s)s, and the
solid phase density s.

For saturated porous media, the liquid volume fraction l is equal to the porosity p,
but for unsaturated porous media, they are related by the saturation s as l = psThe
resulting gas volume fraction in the case of an unsaturated porous medium is

 g =  p –  l =  1 – s  p

On the right-hand side of Equation 6-26, 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 6-26 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.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 351

 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 
  c  =  c P i c i – c   p = K P,i i – c P i  s p (6-27)
t P i  ci  t P i s  t 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  g c i  g
 =  + k c =  g k G i + k G i c i (6-28)
c
 t g G i
g  ci  t G  i i t 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,l = p, and the governing
equations are

 
 c  +   c P i  + u  c i =     D D i + D e i  c i  + R i + S i (6-29)
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

352 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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
p
u
u a = ---- Unsaturated
l

where p is the porosity and l = sp the liquid volume fraction, and s the saturation,
a dimensionless number between 0 and 1.

Figure 6-2: 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 6-26 is written as:

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 353

   
 c  +   c P i  + ( g c G i) +   uc i =
t l i t t (6-30)
    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 6-26.

When using the nonconservative formulation, which is the default, the fluid is assumed
incompressible and divergence free:  u = . 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
p
D e = ----- D L Saturated Porous Media
L
l
D e = ----- D L Unsaturated Porous Media
L
l g
D e = ----- D L + ------ k G D G Unsaturated with Volatilization
L G

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 F, L, and
G 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

354 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

–7  3 2 –7  3 2
L = l p , G = g p

and Bruggeman model

–5  2 2 –5  2 2
L = l p , G = g p

For saturated porous media l = p. The fluid tortuosity for the Millington and Quirk
model is

–1  3
L = p

and for the Bruggeman model the tortuosity is defined as

–1  2
L = p

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.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 355

 Figure 6-3: 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 =  L ------ +  T ------
u u

ui uj
D Dij = D Dji =   L –  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 L and T
(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:

356 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 2 2 2
u v w
D Lxx =  1 ------ +  2 ------ +  3 -------
u u u
2 2 2
v u w
D Lyy =  1 ------ +  2 ------ +  3 -------
u u u
2 2 2
w u v
D Lzz =  1 ------- +  3 ------ +  3 ------
u u u (6-31)
uv
D Lxy = D Lyx =   1 –  2  -------
u
uw
D Lxz = D Lzx =   1 –  3  --------
u
vw
D Lyz = D Lzy =   1 –  3  --------
u

In Equation 6-31 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 1 (SI unit: m) is the
longitudinal dispersivity. If z is the vertical axis, 2 and 3 are the dispersivities in the
transverse horizontal and transverse vertical directions, respectively (SI unit: m).
Setting 2 = 3 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:

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 357

 KL c
c P = c Pmax -------------------- Langmuir
1 + KL c
c N
c P = K F  -------- Freundlich
 c ref
bT c (6-32)
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
cS

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

 b c P ua
RF = 1 + ----- -------- = -----
 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.

358 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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 . Similarly, solid phase reaction
expressions include the bulk density, b, and gas phase reactions include the gas
volume fraction, av.

The following expressions define some common types of reactions:

ln 2
R Li = –  --------- c i Radioactive decay — liquid
 Li
ln 2 c Pi
R Pi = –  b ---------  ---------- c i Radioactive decay — solid
 Pi  c i 
c Gi
R Gi = – --------- a v  ----------- c i Radioactive decay — gas
ln 2
 Gi c
R Lk =  Li c i Creation from parent c Li — liquid
c Pi
R Pk =  b  Pi  ---------- c i Creation from sorbed parent c Pi — solid
 c i 
c Gi
R Gk = – a v  ----------- c i Reaction — gas
 c 

where  is the chemical half life, 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 
 T =  R exp ------------------------------ (6-33)
R u TT R

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 359

 In Equation 6-33, 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):


u = ---  t p


Here u is the tangential Darcy velocity,  is the fracture permeability, 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 6-26. The resulting equation is:

 b c P i  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 (6-34)
 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), p 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

360 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Using , 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 6-34. 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.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 361

 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.

362 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Theory for the Transport of
Concentrated Species Interface
The Transport of Concentrated Species Interface theory is described in this section:

• Multicomponent Mass Transport

• Multicomponent Gas Diffusion: Maxwell–Stefan Description
• Multicomponent Diffusivities
• Multicomponent Diffusion: Mixture-Averaged Approximation
• Multispecies Diffusion: Fick’s Law Approximation
• Multicomponent Thermal Diffusion
• Regularization of Reaction Rate Expression
• References for the Transport of Concentrated Species Interface

Multicomponent Mass Transport

Suppose a reacting flow consists of a mixture with i1, …, Q species and j = 1, …, N
reactions. Equation 6-35 then describes the mass transport for an individual species:

 
 i  +     i u  = –   j i + R i (6-35)
t

where,  (SI unit: kg/m3) denotes the mixture density and u (SI unit: m/s) the mass
averaged velocity of the mixture. The remaining variables are specific for each of the
species, i, being described by the mass transfer equation:

• i is the mass fraction (1)

• ji (SI unit: kg/(m2·s)) is the mass flux relative to the mass averaged velocity, and
• Ri (SI unit: kg/ (m3·s)) is the rate expression describing its production or
consumption.

The relative mass flux vector ji can include contributions due to molecular diffusion,
mass flux due to migration in an electric field, and thermal diffusion.

Summation of the transport equations over all present species gives Equation 6-36 for
the conservation of mass

THEORY FOR THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 363

 
+    u  = 0 (6-36)
t

assuming that

Q Q Q

 i = 1,  ji = 0,  Ri = 0
i=1 i=1 i=1

Using the mass conservation equation, the species transport for an individual species,
i, is given by:

    i  +   u    i = –   j i + R i (6-37)
t

Q  1 of the species equations are independent and possible to solve for using
Equation 6-37. To compute the mass fraction of the remaining species, COMSOL
Multiphysics uses the fact that the sum of the mass fractions is equal to 1:

1 = 1 –  i (6-38)
i=2

Multicomponent Gas Diffusion: Maxwell–Stefan Description

In a multicomponent mixture, the mass flux relative to the mass average velocity, ji,
can be defined by the generalized Fick equations (Ref. 1):

 D̃ik dk – Di  ln T
T
j i = –  i (6-39)
k=1

In Equation 6-39:
˜ (SI unit: m2/s) are the multicomponent Fick diffusivities
• D ik

• T (SI unit: K) is the temperature

T
• D i (SI unit: kg/ m·s)) are the thermal diffusion coefficients, and
• dk (SI unit: 1/m) is the diffusional driving force acting on species k.

For ideal gas mixtures the diffusional driving force is (Ref. 1)

364 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 Q
1
d k = -------------- p k –  k p –  k g k +  k
cR g T  l gl (6-40)
l=1

where

• c (SI unit: mol/m3) is the total molar concentration

• Rg is the universal gas constant 8.314 J/(mol·K)
• p (SI unit: Pa) is the total pressure
• pk (SI unit: Pa) is the partial pressure, and
• k (SI unit: kg/m3) is the density of species k, and
• gk (SI unit: m/s2) is an external force (per unit mass) acting on species k. In the
case of an ionic species the external force arises due to the electric field.
As can be seen in Equation 6-39 and Equation 6-40, the total diffusive flux for the
species depends on the gradients of all species concentrations, temperature, and
pressure as well as any external force on the individual species.

Using the ideal gas law, p  c·Rg·T, and the definition of the partial pressures, pk  xkp,
the equation can be written as

Q
1
d k = x k + ---  x k –  k  p –  k g k +  k
p  l gl (6-41)
l=1

The mole fraction xk is given by

k
x k = -------- M (6-42)
Mk

and the mean molar mass M (SI unit: kg/mol) by

Q
1- i
----
M
=  ------
Mi
-
i=1

When using the Maxwell–Stefan diffusion model, the transport equations for the
species’ mass are

THEORY FOR THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 365

 Q
 
  ˜ d + DT  T-
   i  +   u    i =    i
t 
D ik k
-------
i T  + Ri 
 k=1 
(6-43)
Q
1
d k = x k + ---  x k –  k  p –  k g k +  k
p  l gl
l=1

Multicomponent Diffusivities
˜
The multicomponent Fick diffusivities, D ik , are needed to solve Equation 6-43. The
diffusivities are symmetric

˜ ˜
D ik = D ki

and are related to the multicomponent Maxwell–Stefan diffusivities, Dik, through the
following relation (Ref. 2)

xi xk
  adjB i  jk
ji ˜ –D ˜ ,
---------- = –  i  k ---------------------------------------- ,  B  = D kj ij ij (6-44)
D ik ˜ i kj
 D ij  adjB i  jk
ji

where (adjBi)jk is the jkth component of the adjoint of the matrix Bi.

For low-density gas mixtures, the multicomponent Maxwell–Stefan diffusivities, Dij,

can be replaced with the binary diffusivities for the species pairs that are present.

Solving for Equation 6-44 leads to a number of algebraic expressions for each of the
components in the multicomponent Fick diffusivity matrix. For two- and
three-component systems, these are implemented and solved directly by COMSOL
˜
Multiphysics. For instance, the component D 12 in a ternary system is given by:

1  2 + 3  2  1 + 3   32
– -------------------------------- – -------------------------------- + ----------------
˜ x 1 D 23 x 2 D 13 x 3 D 12
D 12 = --------------------------------------------------------------------------------------------------
x1 x2 x3
-------------------- + -------------------- + --------------------
D 12 D 13 D 12 D 23 D 23 D 13

For four components or more, COMOL Multiphysics obtains the multicomponent

Fick diffusivities numerically through matrix inversion derived from the matrix

366 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

properties defined in Ref. 2. The program starts with the multicomponent Maxwell–
Stefan diffusivity matrix Dik to compute the multicomponent Fick diffusivity matrix,
˜
D ik , using the following equation:

˜ = N –g
D (6-45)
ij ij
˜
where ij are indices in the matrices D and N, and ranges from 1 to the number of
species, Q.

The elements of the matrix N in Equation 6-45 are defined as

–1
N ij =  P  ij (6-46)

where P1 is the inverse of a matrix P defined as

i j ˜
P ij = ------------ – C ij
g
˜
The matrix C in turn is defined as

 xi xj
 --------- ij
˜  D ij
C ij = 

 –  C˜ ik i=j
 kj

The term g in Equation 6-45 is a scalar value that provides numerical stability and
should be of the same order of magnitude as the multicomponent Maxwell–Stefan
diffusion coefficients. The physics interface therefore defines q as the sum of the
multicomponent Maxwell–Stefan diffusion coefficients:

n–1
 n 
g =  

 D ij 

i = 1  j = i+1 

Because the multicomponent Fick diffusivity matrix is symmetric, it is sufficient to

˜
apply Equation 6-46 to the upper triangle elements of D . The remaining elements are
obtained by swapping the indices in the matrix.

THEORY FOR THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 367

 Multicomponent Diffusion: Mixture-Averaged Approximation
The mixture-averaged diffusion model assumes that the relative mass flux due to
molecular diffusion is governed by a Fick’s law type approximation.

Assuming that the diffusive flux, relative to the mass averaged velocity, is proportional
to the mole fraction gradient, the mass flux is defined as:

m x i
j md i = –  i D i --------- (6-47)
xi

Here i is the density, and xi the mole fraction of species i. Using the definition of the
species density and mole fraction

i
 i =  i , x i = ------- M
Mi

Equation 6-47 can be expressed in terms of the mass fractions (i) in the manner of

m M
j md i = –  D i  i +  i D i ---------
m
 M

Using Equation 6-47 together with the Maxwell–Stefan equations, where isobaric and
isothermal conditions have been assumed, the following expression for the
mixture-averaged diffusion coefficients can be derived (Ref. 3):

m 1 – i
D i = -------------------------- (6-48)
xk

N
---------
kiD
ik

If instead the diffusive flux (relative to the mass averaged velocity) is assumed
proportional to the mass fraction gradient, the mass flux is defined as:

m*  i m*
j md i = –  i D i ---------- = – D i  i (6-49)
i

For this assumption, using Equation 6-49 together with the Maxwell–Stefan
equations, also assuming isobaric and isothermal conditions, the following expression
for the mixture-averaged diffusion coefficients can be derived (Ref. 3):

1 xk xi k
k  i --------
D ik 1 –  i k  i D ik
N N
-----------
m*
= - + --------------- --------- (6-50)
Di

368 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

THE MIXTURE-AVERAGED DIFFUSION COEFFICIENT
When using the mixture-averaged model, the diffusion is proportional to a single
diffusion coefficient. The coefficient describes the diffusion of species i relative to the
remaining mixture and is referred to as the mixture-averaged diffusion coefficient. The
coefficient is explicitly given in terms of the multicomponent Maxwell–Stefan
diffusivities Dik. As a consequence, no matrix inversion operation is required as for the
Maxwell–Stefan diffusion model (when using four or more species). For low-density
gas mixtures, the Dik components can be replaced by the binary diffusivities for the
species pairs present.

MIXTURE DIFFUSION CORRECTION

It should be noted that models for the multicomponent diffusivities based on Fick’s
law are approximations. One drawback of this is that the net diffusive mass flux, the
sum of all mass fluxes relative to the mass averaged velocity, is not constrained to zero.
To account for this we add a flux, defined by a correction velocity uc, to enforce a zero
net diffusive flux in the manner of:

i = 1 i  ud,i + uc 
N
j md i = = 0 (6-51)

Hence the correction velocity is:

i = 1 i ud,i
N
uc = – (6-52)

Here ud,i is the diffusion velocity resulting from the flux assumption in Equation 6-47
or Equation 6-49. Note that the correction velocity is a constant correction (same for
all species), but varies in space.

Using the correction velocity together with Equation 6-47, the resulting diffusive flux
is

m M Mi
i = 1 ------
m N m
j md i = – D i  i –  i D i --------- +  i - D x i (6-53)
M M i

If instead Equation 6-49 is used the resulting diffusive flux is

i = 1 Di
m* N m*
j md i = – D i  i +  i  i (6-54)

THEORY FOR THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 369

 ADDITIONAL TRANSPORT MECHANISMS
Apart from molecular diffusion, transport due to thermal diffusion and migration of
charged species in an electric field can be accounted for by adding the following terms
to the diffusive flux:

T T
j i =    D i -------- +  i z i u m i F 
 T 

where
T
• D i (SI unit: kg/(m·s)) is the thermal diffusion coefficient
• zi (dimensionless) is the charge number
• um,i the mobility of the ith species, and
•  (SI unit: V) is the electric potential.

Multispecies Diffusion: Fick’s Law Approximation

Using a Fick’s law approximation, the relative mass flux due to molecular diffusion is
governed by

F x i
j md i = –  i D i kl --------- (6-55)
xi

when assuming that the diffusive flux is proportional to the mole fraction gradient. If
instead assuming that it is proportional to the mass fraction it becomes

F
j md i = – D i kl  i (6-56)
F
In the equations above D i kl represents a general diffusion matrix (SI unit: m2/s)
describing the diffusion of species i into the mixture. This form makes it possible to
use any diffusion coefficient, matrix, or empirical model based on Fick’s law. For
example, in situations when the mass transport is not dominated by diffusion, an
alternative is to use the diffusion coefficients at infinite dilution,

F 0
D i kk = D i

These coefficients are typically more readily available compared to the binary diffusion
diffusivities, especially for liquid mixtures.

370 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

The mixture diffusion correction described above for the mixture-averaged diffusion
can also be applied in this case. Correspondingly, the resulting diffusive flux is

F M Mi
i = 1 ------
F N F
j md i = – D i kl  i –  i D i kl --------- +  i - D x (6-57)
M M i kl i

when using Equation 6-55 and

i = 1 Di kl i
F N F
j md i = – D i kl  i +  i (6-58)

when instead using Equation 6-56.

When using the Fick’s Law approximation, Additional Transport Mechanisms can be
accounted for in the same manner as described above for the mixture-averaged
approximation.

Multicomponent Thermal Diffusion

Mass diffusion in multicomponent mixtures due to temperature gradients is referred
to as the Soret effect. This occurs in mixtures with high temperature gradients and
large variations in molecular weight (or size) of the species. Typically species with high
molecular weight accumulate in lower temperature regions while the diffusion due to
the Soret effect transports species with low molecular weight to higher temperature
regions. In COMSOL Multiphysics, thermal diffusion is included by prescribing the
T
thermal diffusion coefficients D i . In a multicomponent mixture, the sum of the
thermal diffusion coefficients is zero:

 Di
T
= 0
i=1

Regularization of Reaction Rate Expression

The flexibility of COMSOL means that a reaction can result in nearly any reaction rate
contribution Ric to a mass fraction i. But a reactant, r, can physically only be
consumed if r  0 and a product, k, can only be formed if k  1. The Reaction
feature in Transport of Concentrated Species Interface contains a way to regularize
make the rate expression contributions comply to these restrictions.

When selected the “core”, or unregularized reaction rate contribution, Ric, to a mass
fraction i is replaced by

THEORY FOR THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 371

 c c c c
1 Ri – Ri 1 Ri + Ri
R i = --- -------------------------------- max   i 0  + --- -----------------------------------------
- max  1 –  i 0  (6-59)
2 max     dl  2 max  1 –    dl 
i i i i

The first term on the right hand side of Equation 6-59 is active if Ric  0, that is if i
is a reactant. The reaction rate contribution, Ri, is equal to the “core” reaction rate,
Ric, as long as i  idl. As i approaches zero, the regularization damps out negative
Ric and for i  0, Ri for reactant i is equal to zero.

The second term on the right hand side of Equation 6-59 is active if Ric  0, that is if
i is a product. The reaction rate contribution, Ri, is equal to the “core” reaction rate,
Ric, as long as i  1idl. As i approaches one, the regularization damps out
positive Ric and for i  1, Ri for product i is equal to zero.

The damping limits, idl, should be in an order of magnitude that can be considered
numerical noise for species i. The damping limits are per default set to 1e6, which is
appropriate for most applications. It can be advantageous to lower some limits when
working with for example catalytic trace species and the limits can sometimes be raised
to gain additional robustness.

References for the Transport of Concentrated Species Interface

1. C.F. Curtiss and R.B. Bird, “Multicomponent Diffusion”, Ind. Chem. Res., vol. 38
pp. 2515–2522, 1999.

2. R.B. Bird, W.E. Stewart, and E.N. Lightfoot, Transport Phenomena, 2nd ed., John
Wiley & Sons, 2005.

3. R.J. Kee, M.E. Coltrin, and P. Glarborg, Chemically Reacting Flow, John Wiley &
Sons, 2003.

372 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Theory for the Electrophoretic
T r a ns po r t Interfac e
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,  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  l + uc i = J i + uc i (6-60)

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 .

CHARGE BALANCE EQUATION

The current vector, il (A/m2), is defined as

il =  zi Ni (6-61)
i

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

The governing equation for the electrolyte potential is

  il = Ql (6-62)

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

THEORY FOR THE ELECTROPHORETIC TRANSPORT INTERFACE | 373

 N+2

 zi ci = 0 (6-63)
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 (6-64)

This reaction is fast, following the equilibrium relation

2 –6
c H + c OH - = K w  1 mol dm (6-65)

– 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 (6-66)
i=1

Combining these two equations results in the following algebraic expressions for the
concentrations of H+ and OH-.

2
  2 –6
c H + = – --- + ------ + K w  1 mol dm (6-67)
2 4

and

2
  2 –6
c OH - = --- + ------ + K w  1 mol dm (6-68)
2 4

where

 =  zi ci (6-69)
i=1

MASS BALANCE EQUATIONS FOR DISSOCIATION SPECIES

Assume a set of species Si describing k dissociation steps from

374 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 + z +k–1
z +k z +k–1 +  H   S k0– 1 
S k0  S k0– 1 +H K a 1 = ----------------------------------------
z0 + k
(6-70)
 Sk 

to

+ z
z +1 z +  H   S 00 
S k0  S 00 + H K a k = -------------------------
z +1
- (6-71)
 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
(6-72)

 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
(6-73)

if l>m.

Setting m=i and denoting the flux of species i by Ni using equation Equation 6-60,
the mass balance equation for the concentration ci of each subspecies i in the
dissociation chain is

c
-------i +   N i = R eq i k – i – R eq i k – i + 1 + R i (6-74)
t

where Req,i,j is the reaction source stemming from the jth dissociation step (with
Req,i,k+1=0), and Ri any additional reaction sources.

The reaction source contributions from the dissociation steps are generally not known,
but may be canceled by taking the sum of all mass balance equations, resulting in

THEORY FOR THE ELECTROPHORETIC TRANSPORT INTERFACE | 375

 k k
c i
 ------
- +   N i =
  t   Ri (6-75)
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  (1) removed from the molecule.  is typically provided as a
function of pH, based on experimental data. The average charge of the species then is
z = z 0 –  , so that the flux of the species is written as:

N i = – Dc i – zu m Fc i  l + uc i (6-76)

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 –   , is not
2 2 2 2 2 2
equal to the “average squared charge”, z = z 0 + 2z 0  +  = z –  +  (Ref. 1).

The addition to the current density vector is

2
i l =  – F  zD i c i + z u m c i  l  (6-77)

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 2
 = – cH+ + (6-78)
d c H+

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

2 2
z = – c H+ d  + z = – cH+ d z + z
2
(6-79)
d cH+ d cH+

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

kT
r = --------------- (6-80)
6D

376 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

where is the  (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 = -------- (6-81)
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  r  Df  r 
u m = ------------------------------------ = ------------------------------ (6-82)
6F  1 + r  RT  1 + r 

where  (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
 = ----------------- (6-83)
 0 kT
i=1

where  is the dielectric constant of the fluid and 0 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
r = 0 to 1.5 for r =  . 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/, 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
 = -----------------    abs(z i)c i
2 2
zi ci + (6-84)
 0 kT
 i=1 i = N–M+1 

REFERENCES
1 The Dynamics of Electrophoresis, Mosher, Saville and Thormann, VCH
Verlagsgesellschaft mbH, Weinheim, Germany, 1992.

THEORY FOR THE ELECTROPHORETIC TRANSPORT INTERFACE | 377

 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.

378 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

T he o r y f o r th e S u rface R eact i on s
Interface
The Surface Reactions Interface solves for an arbitrary number of surface
concentrations, cs,i (SI unit: mol/m2), referring to species adsorbed on a reactive
surface, and an arbitrary number of bulk concentrations cb,k (SI unit: mol/m3),
referring to the species in the solid material that constitutes the bulk of the reactive
surface.

In this section:

• Governing Equations for the Surface Concentrations

• Governing Equations for the Bulk Concentrations
• ODE Formulations for Surface Concentrations
• Surface Reaction Equations on Deforming Geometries
• Reference for the Surface Reactions Interface

Governing Equations for the Surface Concentrations

Transport of adsorbed species occurs in the tangential direction along the surface. The
Surface Reactions interface models the tangential flux in the surface dimension, the
surface molar flux, Nt,i (SI unit: mol/(m·s)) (the subscript t refers to the tangential
direction), as governed by diffusion according to Fick’s law:

N t i = – D s i  t c s i

where Ds,i (SI unit: m2/s) is the surface diffusion coefficient for species i.

The governing equation for the surface concentrations is written as:

c s i
= –  t  N t i + R s  i (6-85)
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, i
(dimensionless), of the species (with index i).

THEORY FOR THE SURFACE REACTIONS INTERFACE | 379

 Writing the density of sites of the surface as s (SI unit: mol/m2) and the site
occupancy number for each species as i (dimensionless), the surface coverages can be
calculated from:

 i c s i
 i = --------------
s

(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, *, can be
calculated from:

* = 1 –  i
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 = ----------
k

where k 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:

380 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 R b tot =  R b k
k

r b tot =  r b k
k

v b tot =  v b k
k

FRACTIONAL RATES AND VELOCITY

The fractional deposition rates are calculated by:

R b k
R b frac k = ---------------
R b tot

r b k
r b frac k = -------------
r b tot

v b k
v b frac k = --------------
v b tot

The fractional deposition rates can be used as measures of the local

fractional composition in a deposited layer at a certain thickness or time.

ACCUMULATED BULK QUANTITIES

By solving for the bulk species concentrations for each time step, the accumulated mass
and thickness changes of the bulk material can be calculated.

The bulk concentration, cb,k (SI unit: mol/m2), for species k is governed by the
equation:

c b k
= R b k (6-86)
t

The bulk concentration in mass basis, mb,k (SI unit: kg/m2) for a species k, can be
derived from:

m b k = M k c b k

THEORY FOR THE SURFACE REACTIONS INTERFACE | 381

 leading to the bulk thickness sb,k (SI unit: m) of species k according to:

m b k
s b k = -------------
k

TOTAL BULK QUANTITIES

The total bulk concentration is calculated according to:

c b tot =  c b k
k

The deposited total mass, mb,tot (SI unit: kg/m2) is

m b tot =  m b k
k

and the total bulk thickness, stot (SI unit: m) is

s b tot =  sk
k

FRACTIONAL QUANTITIES
The fractional bulk concentration, bulk mass, and thickness (all dimensionless) are
calculated according to:

c b k
c b frac k = -------------
c b tot

m b k
m b frac k = ----------------
m b tot

s b k
s b frac k = -------------
s b tot

ODE Formulations for Surface Concentrations

The surface of a 1D geometry has a 0 dimension, hence no surface transport can be
modeled and the governing equation is reduced to an ODE:

382 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 c s i
= R s i
t

Surface Reaction Equations on Deforming Geometries

If a Surface Reaction interface is used in conjunction with a Deformed Geometry or a
Moving Mesh (ale) interface, the boundary concentration can either be assumed to be
transported with the deforming geometry (moving mesh), with no compensation for
the stretching (the Compensate for boundary stretching check box is not selected), or
the species can be assumed to “float” on the mesh (the Compensate for boundary
stretching check box is selected, which is the default). In the latter case the following
is assumed in 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 6-85
and Equation 6-86, 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 6-85 and Equation 6-86, respectively:

 t   c s i v t mesh 

 t   c b k v t mesh 

THEORY FOR THE SURFACE REACTIONS INTERFACE | 383

 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.

384 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Theory for the Coupling of Mass
Transport to Electrochemical
Reactions
When relating the species fluxes at an electrode surface to the electrical currents, the
general chemical reaction formula

 ox Sox + ne  red Sred

-

ox red

is used to define the stoichiometric coefficients, i, with i being positive (red) for
products and negative (ox) 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:

 i m i m
Ni =  -----------------
nm F
-
m

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

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

Ni = Ni  n

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

THEORY FOR THE COUPLING OF MASS TRANSPORT TO ELECTROCHEMICAL REACTIONS | 385

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

 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.

386 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Theory for the Reacting Flow
Interface
The following sections describe theory applicable for the Reacting Flow interface:

• Pseudo Time Stepping for Mass Transport

• The Stefan Velocity
• The Chemical Reaction Rate

Pseudo Time Stepping for Mass Transport

In order to improve the solution robustness, pseudo time stepping can be used for the
Transport of Concentrated Species interface when solving a stationary model. Using
pseudo time stepping, a fictitious time derivative term:

 i – nojac   i 
 ------------------------------------
t̃

is added to the left-hand side of the mass fraction equations. Here  is the fluid mixture
density, i is the mass fraction (dimensionless) of species i, and t̃ is the pseudo time
step. Since inojac(i) 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 time step of size t̃ .

For a description of the pseudo time step term for the Navier-Stokes
equations and the pseudo time step see and Pseudo Time Stepping in the
COMSOL Multiphysics Reference Manual.

The Stefan Velocity

Heterogeneous reactions on fluid-solid surfaces can affect the mass, momentum, and
energy balances at the interface separating the fluid and the solid. On the reacting
surface, the production or destruction rate, rs,i (SI unit: mol/(m2·s)), of a fluid phase
species is balanced by the total mass flux of the species. The mass balance for species i
on a boundary representing a fluid-solid interface is given by:

THEORY FOR THE REACTING FLOW INTERFACE | 387

 n   j i +  i u  = r s,i M i (6-87)

Here, n is the unit normal pointing out of the fluid domain, u is the mass averaged
velocity of the fluid mixture (SI unit: m/s), ji denotes the mass flux of species i relative
to relative to the mixture (typically due to diffusion), and Mi is the species molar mass
(SI unit: kg/mol). Summing the mass balances at the surface, over all species, results
in an effective mixture velocity:

n  u s =  rs,i Mi (6-88)
i=1

referred to as the Stefan velocity, here denoted us. To reach Equation 6-88 the fact
that the sum of all mass fractions is one, and that the sum of all relative diffusive fluxes
is zero, was used.

Equation 6-88 implies that surface reactions result in a net flux between the surface
and the domain. A net flux in turn corresponds to an effective convective velocity at
the domain boundary; the Stefan velocity. It should be noted here that when solving
for mass transport inside a fluid domain, an outer boundary of the domain corresponds
to a position just outside of the actual physical wall (on the fluid side). The domain
boundary does not coincide with the physical wall.

In most reacting flow models, the species mass fractions in the fluid domain are solved
for without including the surface concentrations (mol per area) on exterior walls. One
reason for this is that the surface reaction rates are often not known. In this case,
surface reactions can be modeled either by applying a mass flux or prescribing the mass
fraction, or a combination of both, on fluid boundaries adjacent to the reacting
surface. The Stefan velocity on a fluid domain boundary is then defined as the net mass
flux resulting from the boundary conditions applied:

n  u s =  n   j0 i + 0 i u  (6-89)

i=1

Here, the first term contains contributions from boundary conditions prescribing the
mass flux, while the second contains contributions from boundary conditions
prescribing the mass fractions. Contributions to the Stefan velocity can be added by
selecting Account for Stefan velocity in the Flux or Mass Fraction features in The
Transport of Concentrated Species interface.

388 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

The resulting Stefan velocity based on mass transport boundary conditions is
computed as:

 n  j 0 i
n  u s = ------------------------------------
i=1 - (6-90)
N
 
 1 –   i 0
 
 i 

Using a Reacting Flow interface, the Stefan velocity, defined in the manner of
Equation 6-90, is automatically computed and applied on boundaries corresponding
to walls in the coupled fluid flow interface. The Stefan velocity is prescribed in the wall
normal direction on the wall selection.

The Chemical Reaction Rate

For laminar flow, or when the Turbulent-reaction model is set to None in a feature (in
Transport of Concentrated Species), the default (Automatic) reaction rate used by the
feature is based on the mass action law. Consider a general reaction belonging to a set
of j reactions and involving i species:

f (6-91)
kj
aA + bB + ... r
xX + yY + ...
kj

For such a reaction set, the reaction rates rj (SI unit: mol/(m3·s)), can be described by
the mass action law:

– 
 
f r
rj = kj c i ij – k j c i ij (6-92)
i  react i  prod
f r
Here, kj and kj denote the forward and reverse rate constants, respectively. The
concentration of species i is denoted ci (SI unit: mol/m3). The stoichiometric
coefficients are denoted ij, and are defined to be negative for reactants and positive
for products. In practice, a reaction seldom involves more than two species colliding
in a reacting step, which means that a kinetic expression is usually of order 2 or less
(with respect to the involved concentrations).

In addition to the concentration dependence, the temperature dependence can be

included by using the predefined Arrhenius expressions for the rate constants:

THEORY FOR THE REACTING FLOW INTERFACE | 389

 k = AT exp  – -----------
n E
 R g T

Here, A denotes the frequency factor, n the temperature exponent, E the activation
energy (SI unit: J/mol) and Rg the gas constant, 8.314 J/(mol·K). The
pre-exponential factor, including the frequency factor A and the temperature factor
Tn, is given the units (m3/mol)  1/s, where  is the order of the reaction (with
respect to the concentrations).

390 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 7

Fluid Flow Interfaces

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

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
• The Bubbly Flow Interface
• The Mixture Model Interface
• The Euler-Euler Model 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 Bubbly Flow Interface
• Theory for the Mixture Model Interface

| 391
 • Theory for the Euler-Euler Interface
• Theory for the Coupling of Fluid Flow to Electrochemical Reactions

392 | CHAPTER 7: FLUID FLOW INTERFACES

The Laminar Flow and Creeping Flow
Interfaces
In this section:

• The Creeping Flow Interface

• The Laminar Flow Interface
• The Bubbly Flow Interface

• Theory for the Coupling of Fluid Flow to Electrochemical Reactions

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.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 393

 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.

394 | CHAPTER 7: FLUID FLOW INTERFACES

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.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 395

 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.

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.

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.

396 | CHAPTER 7: FLUID FLOW INTERFACES

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 id as
a scalar positive value. The default value is 0.25 (a reasonable value to start with is
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

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 397

 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 Coupling of Fluid Flow to Electrochemical Reactions
• Block Navier-Stokes in the COMSOL Multiphysics Reference
Manual.

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

398 | CHAPTER 7: 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 PropertiesInitial Values • Pressure Point Constraint
• Inlet • Symmetry
1
• Line Mass Source • Volume Force
• Open Boundary • Wall
• 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 | 399

 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

400 | CHAPTER 7: 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  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
 +   u   u =   – pI +   u +  u   – ---     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.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 401

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

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.

Slip
The Slip option prescribes a no-penetration condition, u·n. It is implicitly assumed
that there are no viscous effects at the slip wall and hence, no boundary layer develops.
From a modeling point of view, this can be a reasonable approximation if the main
effect of the wall is to prevent fluid from leaving the domain.

Leaking Wall
This boundary condition may be used to simulate a wall where fluid is leaking into or
leaving the domain with the velocity u = ul through a perforated wall. The
components of the Fluid velocity ul on the leaking wall should be specified.

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


K nt = – --- u slip


402 | CHAPTER 7: FLUID FLOW INTERFACES

where K nt = K n –  K n  n wall n wall , K n = Kn wall and K is the viscous stress tensor.
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  is then defined as  = 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 (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
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; that is,
the surface is sliding in its 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

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 403

 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
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 and Pressure. After
selecting a Boundary Condition from the list, a section with the same or a similar name

404 | CHAPTER 7: FLUID FLOW INTERFACES

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.

• The Pressure list has two options, Static and Total.

- If Pressure is Static, and the reference pressure pref, defined at the physics
interface level, is equal to , 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.
• 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.
• 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

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 405

 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
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

406 | CHAPTER 7: FLUID FLOW INTERFACES

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
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.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

• Normal Stress Boundary Condition

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 407

 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.

BOUNDARY CONDITION
The available Boundary condition options for an outlet are Pressure 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.

• The Pressure list has two options, Static and Total.

- If Pressure is Static, and the reference pressure pref, defined at the physics
interface level, is equal to , 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.
• 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.

408 | CHAPTER 7: FLUID FLOW INTERFACES

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
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. 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)

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 409

 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 +    u +  u  T  – 2
---     u I  n = 0
  3 

u  n = 0,  – pI +   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 =   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.

410 | CHAPTER 7: FLUID FLOW INTERFACES

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:

   u +  u  T  – 2
---     u I n = 0
 3 

  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 +    u +  u  T  – 2
---     u I  n = F
  3 

 – pI +   u +  u  T  n = F

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 411

 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 = 2 ---------- – n  F (7-1)
n

If unn is small, Equation 7-1 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 +    u +  u  T  – ---     u I  n = – f 0 ,
T 2
tu = 0
3

T
n  – pI +   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 = 2 ---------- + f 0 (7-2)
n

If unn is small, Equation 7-2 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

412 | CHAPTER 7: FLUID FLOW INTERFACES

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.

PRESSURE DIFFERENCE
This section is available when Incompressible flow is selected for Compressibility under
the Physical Model section for the physics interface.

A value or expression should be specified for the Pressure difference, psrc  pdst. 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.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 413

 A Wall subnode is added by default and it applies to the parts of the pair boundaries
where a source boundary lacks a corresponding destination boundary and vice versa.
The Wall feature can be overridden by any other boundary condition that applies to
exterior boundaries. By right-clicking the Flow Continuity node, additional Fallback
feature subnodes can be added.

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. Or, 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

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).

414 | CHAPTER 7: FLUID FLOW INTERFACES

SOURCE STRENGTH
ꞏ
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
2D Axisymmetry Points not on the axis of symmetry
3D Edges

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 415

 SOURCE STRENGTH
ꞏ
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
This feature requires at least one of the following licenses: CFD Module, Heat Transfer
Module, Microfluidics Module, Polymer Flow Module, Porous Media Flow Module,
or Subsurface Flow Module.

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.

416 | CHAPTER 7: FLUID FLOW INTERFACES

The Darcy’s Law Interface
The Darcy’s Law (dl) interface ( ), found under the Porous Media and Subsurface Flow
branch ( ) when adding a physics interface, is used to simulate fluid flow through
interstices in a porous medium. It can be used to model low-velocity flows or media
where the permeability and porosity are very small, and for which the pressure gradient
is the major driving force and the flow is mostly influenced by the frictional resistance
within the pores. Set up multiple Darcy's Law interfaces to model multiphase flows
involving more than one mobile phase. The Darcy’s Law interface can be used for
stationary and time-dependent analyses.

The main feature is the Fluid and Matrix Properties node, which provides an interface
for defining the fluid material along with the porous medium properties.

When this physics interface is added, the following default nodes are also added in the
Model Builder — Fluid and Matrix Properties, No Flow (the default boundary condition),
and Initial Values. Then, from the Physics toolbar, add other nodes that implement, for
example, boundary conditions and mass sources. You can also right-click Darcy's Law
to select physics features from the context menu.

SETTINGS
The Label is the default physics interface name.

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

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

PHYSICAL MODEL
Enter a Reference pressure level pref (SI unit: Pa). The default value is 1[atm].

GRAVITY EFFECTS
This feature requires a specific license. For a detailed overview of the functionality
available in each product visit https://www.comsol.com/products/specifications/.

THE DARCY’S LAW INTERFACE | 417

 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.

Enter a value for the acceleration of gravity. The default value g_const is the
predefined standard acceleration of gravity on Earth.

For a detailed overview of the functionality available in each product, visit

https://www.comsol.com/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.

418 | CHAPTER 7: FLUID FLOW INTERFACES

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).

THE DARCY’S LAW INTERFACE | 419

 DOMAIN

• Fluid and Matrix Properties • Mass Source

• Gravity • Poroelastic Storage
• Initial Values • Porous Electrode Coupling
• Storage Model • Richards’ Equation Model

Note that some features are only available with certain COMSOL products (see
https://www.comsol.com/products/specifications/).

BOUNDARY, EDGE, AND POINT

The following nodes (listed in alphabetical order) are available on exterior boundaries:

• Atmosphere/Gauge • Outlet
• Cross Section • Pervious Layer
• Electrode Surface Coupling • Point Mass Source
• Flux Discontinuity • Precipitation
• Fracture Flow • Pressure
• Hydraulic Head • Pressure Head
• Inlet • Reaction Coefficients1
• Interior Wall • Symmetry
• Line Mass Source • Thickness
• Mass Flux • Thin Barrier
• 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
https://www.comsol.com/products/specifications/)!

The relevant physics interface condition at interior boundaries is continuity:

n   1 u1 –2 u2  = 0

420 | CHAPTER 7: FLUID FLOW INTERFACES

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.

Fluid and Matrix Properties

The Fluid and Matrix Properties node adds the equations for Darcy’s law, Equation 7-3
and Equation 7-4 (excluding any mass sources), and contains settings for the fluid
properties and the porous matrix properties such as the effective porosity.

    +    u  = Q
(7-3)
t m

THE DARCY’S LAW INTERFACE | 421

 
u = – --- p (7-4)


And if gravity effects are active Darcy’s law is of the following form:


u = – ---  p + g  (7-5)


FLUID PROPERTIES
Select the Fluid material to use for the fluid properties. Select Domain material (the
default) to use the material defined for the domain. Select another material to use that
material’s properties for the fluid.

Density
The default Density  (SI unit: kg/m3) uses values From material based on the Fluid
material selection.

• For User defined enter another value or expression. The default is 0 kg/m3.
• For Ideal gas it uses the ideal gas law to describe the fluid. In this case, specify the
thermodynamics properties. Select a Gas constant type — Specific gas constant Rs
(the default) or Mean molar mass Mn (SI unit: J/(mol·K)). For Mean molar mass the
universal gas constant R  8.314 J/(mol·K) is used as the built-in physical constant.
For both properties, the defaults use values From material. For User defined enter
another value or expression.

Dynamic Viscosity
Select a Dynamic viscosity (SI unit: Pa·s). The default uses values From material as
defined by the Fluid material selected. For User defined the default is 0 Pa·s.

If the settings for the dynamic viscosity are unavailable, this is due to Hydraulic
conductivity being selected as the Permeability model under the Matrix Properties
section below. The hydraulic conductivity is defined using a combination of fluid and
matrix properties and replaces the need to define the dynamic viscosity. Note that this
option is only available with the Subsurface Flow Module.

MATRIX PROPERTIES
Select the material to use as porous matrix. Select Domain material from the Porous
material list (the default) to use the material defined for the porous domain. Select
another material to use that material’s properties.

The default Porosity p (a dimensionless number between 0 and 1) uses the value From
material, defined by the Porous material selected. For User defined the default is 0.

422 | CHAPTER 7: FLUID FLOW INTERFACES

Select a Permeability model to specify the capacity of the porous material to transmit
flow — Permeability to define the permeability of the porous matrix, Hydraulic
conductivity to define a combination of fluid permeability and dynamic viscosity,
Kozeny-Carman to define the permeability from the porosity and mean particle
diameter, or Non-Darcian in cases when Darcy’s linear relation between pressure drop
and velocity is no longer valid due to turbulence or inertial effects.

Note that the option to choose Hydraulic conductivity is only available for the
Subsurface Flow Module. The Non-Darcian Flow option is only available in some
modules. For a detailed overview of the functionality available in each product, visit
https://www.comsol.com/products/specifications/.

The default Permeability (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 Hydraulic conductivity K (SI unit: m/s) select Isotropic to define a scalar value or
Diagonal, Symmetric, or Full to define a tensor value. The default is 2.94·104 m/s.

For Kozeny–Carman, enter the mean Particle diameter dp (SI unit: m), the default value
is 0.5 mm.

For Non-Darcian, choose a Non-Darcian flow model from the selection list. The available
options, depending on the modules licensed, are Forchheimer, Ergun, Burke–Plummer,
and Klinkenberg.

For Forchheimer, the default Permeability (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). The
permeability  is then calculated using Equation 2-4 in the Porous Media Flow
Module User’s Guide.

For Burke–Plummer, specify the mean Particle diameter dp (default value: 0.5 mm).

If Klinkenberg is selected from the list, the default Permeability (SI unit: m2) uses
the value From material, as defined by the Porous material list. Enter the Klinkenberg

THE DARCY’S LAW INTERFACE | 423

 parameter bK. Its default value is 1e3 Pa. The corrected permeability  is then
calculated using Equation 2-7 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 Qm, which appears on the right-hand side of
the Darcy’s Law equation (Equation 7-3).

    +    u 
= Qm (7-6)
t

For the — 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).

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
g

where  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).

424 | CHAPTER 7: FLUID FLOW INTERFACES

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.

Storage Model
The Storage Model node adds Equation 7-4 and Equation 7-42 (excluding any mass
sources). Use it to define the fluid and porous media properties, including a storage
term for the specific storage.

This feature requires a specific license. For a detailed overview of the functionality
available in each product visit https://www.comsol.com/products/specifications/.

FLUID PROPERTIES
The settings are the same as for the Fluid and Matrix Properties node except a gas
constant type is not required.

MATRIX PROPERTIES
The settings are the same as in the Matrix Properties section under Fluid and Matrix
Properties.

STORAGE MODEL
Select a Storage S (SI unit: 1/Pa) — Linearized storage (the default) or User defined.

• For User defined enter a value or expression for Storage S (SI unit: 1/Pa) (Sf in
Equation 7-9).
• For Linearized storage it uses the following linear equation to define the storage:

S =  f +  1 –  p  p

This is equivalent to the Reuss average of the fluid and solid compressibilities. Enter
the value or expression for each of the following:
- Compressibility of fluid f (SI unit: 1/Pa). The default uses values From material.
For User defined, the default is 4·1010 1/Pa.
- Effective compressibility of matrix p (SI unit: 1/Pa). The default is 1·104 1/Pa).

THE DARCY’S LAW INTERFACE | 425

 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

Richards’ Equation Model

The Richards’ Equation Model node defines the storage and retention models in variably
saturated porous media. See the Richards’ Equation Model described for the Richards’
Equation interface.

This feature requires a specific license. For a detailed overview of the functionality
available in each product visit https://www.comsol.com/products/specifications/.

Poroelastic Storage
The Poroelastic Storage node adds Equation 7-4 and Equation 7-42 (excluding any
mass sources). Use it to define the fluid and porous media properties, including a
storage term to account for the Poroelasticity multiphysics coupling.

This feature requires a specific license. For a detailed overview of the functionality
available in each product visit https://www.comsol.com/products/specifications/.

FLUID PROPERTIES
The settings are the same as for the Storage Model node except a gas constant type is
not required. There is also an option to define the fluid compressibility.

Compressibility
Select the Compressibility of fluid f (SI unit: 1/Pa). The default uses values From
material as defined by the Fluid material selected. For User defined the default is
4·1010 1/Pa.

MATRIX PROPERTIES
The settings are the same as in the Matrix Properties section under Fluid and Matrix
Properties.

426 | CHAPTER 7: FLUID FLOW INTERFACES

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 https://www.comsol.com/products/specifications/.

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.

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.

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.

THE DARCY’S LAW INTERFACE | 427

 This feature requires a specific license. For a detailed overview of the functionality
available in each product visit https://www.comsol.com/products/specifications/.

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 https://www.comsol.com/products/specifications/.

SPECIES
Based on the number of species required for the model, use the Add ( ) and
Delete ) buttons under the table to add or remove Species. Then enter a value for
the Molar mass (kg/mol) in the applicable rows for each species.

The setting in the table will determine the number of available field for entering the
stoichiometric coefficients of the Reaction Coefficient subnodes.

Pressure
Use the Pressure node to specify the pressure on a boundary. In many cases the
distribution of pressure is known, giving a Dirichlet condition p = p0 where p0 is a
known pressure given as a number, a distribution, or an expression involving time, t,
for example.

428 | CHAPTER 7: FLUID FLOW INTERFACES

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:


n   ---  p +  g D  = N 0


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)).

Line Mass Source

The Line Mass Source node adds mass flow originating from a tube of infinitely small
radius.

THE DARCY’S LAW INTERFACE | 429

 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.

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:

430 | CHAPTER 7: FLUID FLOW INTERFACES

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;


n   ---  p +  g D  = U 0


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:

–    u  n  dS = M0


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:


n   ---  p +  g D  = N 0


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.

THE DARCY’S LAW INTERFACE | 431

 Symmetry
The Symmetry node describes a symmetry boundary. The following condition
implements the symmetry condition on an axis or a flow divide:


n  --- p = 0



n  ---  p +  g D  = 0


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:


n   ---  p +  g D  = 0


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   u 1 –  u 2  = N 0

In this equation, n is the vector normal (perpendicular) to the interior boundary,  is

the fluid density, u1 and u2 are the Darcy velocities in the adjacent domains (as defined
in Equation 7-7) and N0 is a specified value or expression for the flux discontinuity.


u = – --- p (7-7)


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.

432 | CHAPTER 7: FLUID FLOW INTERFACES

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 two 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.


– n   --- p = U 0


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).

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 https://www.comsol.com/products/specifications/.

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.

THE DARCY’S LAW INTERFACE | 433

 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.

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 https://www.comsol.com/products/specifications/.

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 https://www.comsol.com/products/specifications/.

434 | CHAPTER 7: FLUID FLOW INTERFACES

WALL
Enter a value or expression for the Thickness db (SI unit: m, the default is 0.1 m) and
for the Permeability b(SI unit: m2). The default Permeability b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.

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
https://www.comsol.com/products/specifications/).

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
https://www.comsol.com/products/specifications/).

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.

THE DARCY’S LAW INTERFACE | 435

 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
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 f 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
https://www.comsol.com/products/specifications/).

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
https://www.comsol.com/products/specifications/).

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:

  pb – p 
n   ---  p +  g D  = R b -------------------- +  D b – D  (7-8)
 g

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.

436 | CHAPTER 7: FLUID FLOW INTERFACES

When the pressure head Hp is specified instead of the pressure, the boundary condition
is the following:

n  K  H p + D  = R b   H pb – H p  +  D b – D   (7-9)

Hpb is the pressure head (SI unit: m) at the edge of the layer.

When the hydraulic head H is specified instead of the pressure head, the boundary
condition becomes:

n  KH = R b  H b – H  (7-10)

Hb is the hydraulic head (SI unit: m) at the edge of the layer.

K in Equation 7-9 and Equation 7-10 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).

THE DARCY’S LAW INTERFACE | 437

 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.

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 https://www.comsol.com/products/specifications/.

438 | CHAPTER 7: FLUID FLOW INTERFACES

The Free and Porous Media Flow
Interface
The Free and Porous Media Flow (fp) interface ( ), found under the Porous Media and
Subsurface Flow branch ( ) when adding a physics interface, is used to compute fluid
velocity and pressure fields of single-phase flow where free flow is connected to porous
media. The Free and Porous Media Flow interface is used over at least two different
domains: a free channel and a porous medium. The physics interface is well suited for
transitions between slow flow in porous media, governed by the Brinkman equations,
and fast flow in channels described by the Navier–Stokes equations. Fluids with varying
density can be included at Mach numbers below 0.3. Also the viscosity of a fluid can
vary, for example, to describe non-Newtonian fluids. The physics interface can be used
for stationary and time-dependent analyses.

When this physics interface is added, the following default nodes are also added in the
Model Builder — Fluid Properties, Wall, and Initial Values. Then, from the Physics
toolbar, add a Fluid and Matrix Properties node to be used on the domain selection
corresponding to the porous media, or add other nodes that implement, for example,
boundary conditions and volume forces. You can also right-click Free and Porous Media
Flow to select physics features from the context menu.

SETTINGS
The Label is the default physics interface name.

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

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

PHYSICAL MODEL

Compressibility
By default the physics interface uses the Incompressible flow formulation of the Navier–
Stokes and Brinkman equations to model constant density flow. If required, select
Compressible flow (Ma<0.3) from the Compressibility list, to account for small variations

THE FREE AND POROUS MEDIA FLOW INTERFACE | 439

 in the density, typically dependent on the temperature (nonisothermal flow). For
compressible flow modeled with this physics interface, the Mach number must be
below 0.3.

Neglect Inertial Term

Select the Neglect inertial term (Stokes flow) check box if the inertial forces are small
compared to the viscous forces.

Reference Pressure Level

Enter a Reference pressure level pref (SI unit: Pa). The default value is 1[atm].

Reference Temperature
Enter a Reference temperature Tref (SI unit: K). The default value is 293.15[K].

DEPENDENT VARIABLES
The following dependent variables (fields) are defined for this physics interface — the
Velocity field u (SI unit: m/s) and its components, and the Pressure p (SI unit: Pa).

• Domain, Boundary, Point, and Pair Nodes for the Free and Porous
Media Flow Interface
• Theory for the Free and Porous Media Flow Interface

Current Density Distribution in a Solid Oxide Fuel Cell: Application

Library path Fuel_Cell_and_Electrolyzer_Module/Fuel_Cells/sofc_unit_cell

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.

440 | CHAPTER 7: FLUID FLOW INTERFACES

 • Electrode Surface Coupling • Porous Electrode Coupling
• Fluid Properties • Fluid and Matrix Properties
• Initial Values • Mass Source
• Mass Source • Volume Force
• Wall

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  (SI unit: kg/m3) uses values From material based on the Fluid
material selection. For User defined enter another value or expression. The default is
0 kg/m3.

The Dynamic viscosity  (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.

THE FREE AND POROUS MEDIA FLOW INTERFACE | 441

 Fluid and Matrix Properties
Use the Fluid and Matrix Properties node to define which domains contain porous
material and to define the porous matrix properties, such as the porosity and
permeability in these domains.

DOMAIN SELECTION
Choose domains from the Selection list, to solve for porous media flow governed by
the Brinkman equations. In the domains not selected, the Free and Porous Media Flow
interface solves for laminar flow governed by the Navier–Stokes (or Stokes) equations.

POROUS MATRIX PROPERTIES

The default Porous material uses the Domain material for the porous matrix. Select
another material as needed.

The Porosity p (a dimensionless number between 0 and 1) uses by default the value
From material as defined by the Porous material selection. For User defined the default
is 0.

In this node you specify the porosity p, whereas in other nodes the
volume fraction of solid material p  1  p is required instead. See
Porous Medium in the Heat Transfer Module User’s Guide for an
example.

Select a Permeability model to specify the capacity of the porous material to transmit
flow — Permeability to directly enter the permeability of the porous matrix,
Kozeny-Carman to define the permeability from the porosity and mean particle
diameter, or Non-Darcian in cases when Darcy’s linear relation between pressure drop
and velocity is no longer valid due to turbulence or inertial effects. The Non-Darcian
Flow option 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://www.comsol.com/products/specifications/.

The default Permeability (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.

442 | CHAPTER 7: FLUID FLOW INTERFACES

For Non-Darcian, choose a Non-Darcian flow model from the selection list. The available
options, which depend on the modules licensed, are Forchheimer or Ergun.

For Forchheimer, the default Permeability (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). The
permeability  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.

Effective Mass Transport Parameters

A correction factor (Bruggeman, No Correction, or User defined) to the mass transport
parameters (defined in the Transport Properties node) can be applied for the porous
domain. Species diffusivities and mobilities are automatically adjusted by the porous
media corrections. For User defined enter a value or expression for the Conversion factor
feff. The default is 1. Species diffusivities and mobilities are automatically adjusted by
the porous media corrections.

Volume Force
The Volume Force node specifies the force F on the right-hand side of the Navier–
Stokes or Brinkman equations, depending on whether the Porous Matrix Properties
node is active for the domain. Use it, for example, to incorporate the effects of gravity
in a model.

VOLUME FORCE
Enter the components of the Volume force F (SI unit: N/m3).

THE FREE AND POROUS MEDIA FLOW INTERFACE | 443

 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.

The setting in the table will determine the number of available fields for entering the
stoichiometric coefficients of the Reaction Coefficient subnodes.

Initial Values
The Initial Values node adds initial values for the velocity field and the pressure that can
serve as an initial condition for a transient simulation or as an initial guess for a
nonlinear solver.

INITIAL VALUES
Enter initial values or expressions for the Velocity field u (SI unit: m/s) and for the
Pressure p (SI unit: Pa). The default values are 0 m/s and 0 Pa, respectively.

Electrode-Electrolyte Interface Coupling

Use the Electrode-Electrolyte Interface Coupling node to define a combined wall and
inflow/outflow boundary condition based on current densities of one or multiple
Electrode Reaction nodes in an Electrochemistry interface.

The flow is proportional to the Molar mass (kg/mol) of the reacting species, the current
densities and the stoichiometric coefficients according to Faraday’s law as defined by
summation over the Reaction Coefficient subnodes.

444 | CHAPTER 7: FLUID FLOW INTERFACES

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-, 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. It is implicitly assumed
that there are no viscous effects at the slip wall and hence, no boundary layer develops.
From a modeling point of view, this can be a reasonable approximation if the main
effect of the wall is to prevent fluid from leaving the domain.

Leaking Wall
This boundary condition may be used to simulate a wall where fluid is leaking into or
leaving the domain with the velocity u = ul through a perforated wall. The
components of the Fluid velocity ul on the leaking wall should be specified.

THE FREE AND POROUS MEDIA FLOW INTERFACE | 445

 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

446 | CHAPTER 7: FLUID FLOW INTERFACES

The Brinkman Equations Interface
The Brinkman Equations (br) interface ( ), found under the Porous Media and
Subsurface Flow branch ( ) when adding a physics interface, is used to compute fluid
velocity and pressure fields of single-phase flow in porous media in the laminar flow
regime. The physics interface extends Darcy’s law to describe the dissipation of the
kinetic energy by viscous shear, similar to the Navier–Stokes equations. Fluids with
varying density can be included at Mach numbers below 0.3. Also the viscosity of a
fluid can vary, for example, to describe non-Newtonian fluids. To simplify the
equations, select the Stokes–Brinkman flow feature to reduce the dependence on
inertial effects when the Reynolds number is significantly less than 1. The physics
interface can be used for stationary and time-dependent analyses.

The main node is the Fluid and Matrix Properties feature, which adds the Brinkman
equations and provides an interface for defining the fluid material and the porous
matrix.

When this physics interface is added, the following default nodes are also added in the
Model Builder — Fluid and Matrix Properties, Wall (the default boundary type, using No
slip as the default boundary condition), and Initial Values. Then, from the Physics
toolbar, add other nodes that implement, for example, boundary conditions and
volume forces. You can also right-click Brinkman Equations to select physics features
from the context menu.

The boundary conditions are essentially the same as for the Laminar Flow interface.
Differences exist for the following boundary types: Outlet, Symmetry, Open
Boundary, and Boundary Stress where the viscous part of the stress is divided by the
porosity to appear as

1-  T 2 
----   u +  u   – ---     u I 
 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.

THE BRINKMAN EQUATIONS INTERFACE | 447

 SETTINGS
The Label is the default physics interface name.

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

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

PHYSICAL MODEL
This node specifies the properties of the Brinkman Equations interface, which describe
the overall type of fluid flow model.

Compressibility
By default the physics interface uses the Incompressible flow formulation of the
Brinkman equations to model constant density flow. Alternatively, select Compressible
flow (Ma<0.3) from the Compressibility list if there are small variations in the density,
typically dependent on the temperature (nonisothermal flow). For compressible flow
modeled with the Brinkman Equations interface, the Mach number must be below
0.3.

Neglect Inertial Term (Stokes–Brinkman Flow)

The Neglect inertial term (Stokes–Brinkman) check box is selected by default to model
flow at low Reynolds numbers for which the inertial term can be neglected. This results
in the linear Stokes–Brinkman equations.

Enable porous media domains

The Enable porous media domains check box is selected by default to solve Brinkman
equations in porous domains.

Reference Pressure Level

Enter a Reference pressure level pref (SI unit: Pa). The default value is 1[atm].

DEPENDENT VARIABLES
The following dependent variables (fields) are defined for this physics interface — the
Velocity field u (SI unit: m/s) and its components, and the Pressure p (SI unit: Pa).

448 | CHAPTER 7: FLUID FLOW INTERFACES

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
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.

THE BRINKMAN EQUATIONS INTERFACE | 449

 These nodes are described in this section:

• Fluid and Matrix Properties • Volume Force

• Initial Values • Fluid Properties
• Mass Source

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.

Fluid and Matrix Properties

The Fluid and Matrix Properties node adds the Brinkman equations: Equation 7-43 and
Equation 7-44 (excluding any mass sources), and provides an interface for defining the
properties of the fluid material and the porous matrix.

FLUID PROPERTIES
The default Fluid material uses the Domain material. Select another material as needed.

Both the default Density  (SI unit: kg/m3) and Dynamic viscosity  (SI unit: Pa·s) use
values From material based on the Fluid material selection. For User defined enter
another value or expression. In this case, the default is 0 kg/m3 for the density and
0 Pa·s for the dynamic viscosity. The dynamic viscosity describes the relationship
between the shear stresses and the shear rate in a fluid. Intuitively, water and air have

450 | CHAPTER 7: FLUID FLOW INTERFACES

a low viscosity, and substances often described as thick, such as oil, have a higher
viscosity. Non-Newtonian fluids have a viscosity that is shear-rate dependent. Examples
of non-Newtonian fluids include yogurt, paper pulp, and polymer suspensions.

POROUS MATRIX PROPERTIES

The default Porous material uses the Domain material for the porous matrix. Select
another material as needed.

The Porosity p (a dimensionless number between 0 and 1) uses by default the value
From material as defined by the Porous material selection. For User defined the default
is 0.

Select a Permeability model to specify the capacity of the porous material to transmit
flow — Permeability to directly enter the permeability of the porous matrix,
Kozeny-Carman to define the permeability from the porosity and mean particle
diameter, or Non-Darcian in cases when Darcy’s linear relation between pressure drop
and velocity is no longer valid due to turbulence or inertial effects. The Non-Darcian
Flow option includes different models, some of them are only available for certain
modules. For a detailed overview of the functionality available in each product, visit
https://www.comsol.com/products/specifications/.

The default Permeability (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.

For Non-Darcian, choose a Non-Darcian flow model from the selection list. The available
options, depending on the modules licensed, are Forchheimer or Ergun.

For Forchheimer, the default Permeability (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.

THE BRINKMAN EQUATIONS INTERFACE | 451

 If Ergun is selected, enter the mean Particle diameter dp (default value: 0.5 mm). The
permeability  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 7-43. 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.

 
   +    u  = Q m (7-11)
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).

Volume Force
Use the Volume Force node to specify the force F on the right-hand side of
Equation 7-44. It then acts on each fluid element in the specified domains. A common
application is to include gravity effects.

-  u
+  u    ----- =
u
----
p   t  p
(7-12)
1 T 2   –1 Q m
–  p +   -----    u +  u   – ---     u I  –    + --------u + F
p  3    p2 

VOLUME FORCE
Enter the components of Volume force F (SI unit: N/m3).

452 | CHAPTER 7: FLUID FLOW INTERFACES

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
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

THE BRINKMAN EQUATIONS INTERFACE | 453

 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  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.

454 | CHAPTER 7: FLUID FLOW INTERFACES

The Bubbly Flow Interface
In this section:

• The Laminar Bubbly Flow Interface

• Domain and Boundary Nodes for Bubbly Flow

The Laminar Bubbly Flow Interface

The Laminar Bubbly Flow (bf) interface ( ), found under the Multiphase Flow>Bubbly
Flow branch ( ) when adding a physics interface, is used to model the flow of liquids
with dispersed bubbles at low and moderate Reynolds numbers.

It is assumed that the bubbles only occupy a small volume fraction and that they always
travel with their terminal velocity. It is thereby possible to solve only one set of
Navier-Stokes equations for the liquid phase and to let the velocity of the bubbles be
guided by a slip model. The pressure distribution is computed from a
mixture-averaged continuity equation. The volume fraction of bubbles is tracked by
solving a transport equation for the effective gas density.

The physics interface can also model the distribution of the number density, that is, the
number of bubbles per unit volume which in turn can be used to calculate the
interfacial area, useful when simulating chemical reactions in the mixture.

The main physics node is the Fluid Properties feature, which adds the equations for
laminar bubbly flow and provides an interface for defining the fluid materials for the
liquid and the gas and the slip velocity model to use.

When this physics interface is added, the following default physics nodes are also added
in the Model Builder — Laminar Bubbly Flow, Fluid Properties, Wall (the default boundary
types are No slip for the liquid and No gas flux for the gas), 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 Laminar Bubbly 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

THE BUBBLY FLOW INTERFACE | 455

 <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 bf.

PHYSICAL MODEL
Specify if the gas concentration is low and whether or not to solve for the interfacial
area.

Low Gas Concentration

The Low gas concentration check box is selected by default. This approximation is valid
if the gas volume fraction is low (  g less than a few percent) and its density does not
have any significant effects on the continuity equation. It is then generally valid to
replace the continuity equation in The Bubbly Flow Equations.

Solve for Interfacial Area

To add a transport equation for the bubble density in order to determine the interfacial
area, select the Solve for interfacial area check box.

Reference Values
Reference values are global quantities used to evaluate the density of the liquid and the
absolute pressure pA.

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 density of the liquid. The default Reference
pressure level pref (SI unit: Pa) is 1[atm].

Reference temperature The reference temperature is used to define the density of the
liquid. The default Reference temperature Tref (SI unit: K) is 293.15[K].

Swirl Flow
For 2D axisymmetric models, select the Swirl flow check box to include the swirl
velocity component — that is, the velocity component u  in the azimuthal direction.
While u  can be nonzero, there can be no gradients in the  direction. Also see in
the CFD Module User’s Guide.

456 | CHAPTER 7: FLUID FLOW INTERFACES

DEPENDENT VARIABLES
The dependent variables (field variables) are the Velocity field, liquid phase u (SI unit:
m/s), the Pressure p (SI unit: Pa), the Effective gas density rhogeff (SI unit: kg/m3),
and the Number density, gas phase nd (SI unit: 1/m3). The names can be changed but
the names of fields and dependent variables must be unique within a component.

CONSISTENT STABILIZATION AND INCONSISTENT STABILIZATION

To display this section, click the Show More Options button ( ) and select Stabilization
in the Show More Options dialog box. This section contains the settings for stabilization
of the momentum transport (the fluid flow) in the Momentum transport area and
stabilization of the equation for the dispersed phase in the Gas phase transport area.

Consistent streamline and crosswind diffusion is applied by default to both gas and
momentum transport. Additional inconsistent stabilization terms may be added when
required as isotropic diffusion.

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 the Use pseudo time stepping for stationary equation form check box to add
pseudo time derivatives to the equation when the Stationary equation form is used.
When selected, also choose a CFL number expression — Automatic (the default) or
Manual. Automatic sets the local CFL number (from the Courant–Friedrichs–Lewy
condition) to the built-in variable CFLCMP which in turn triggers a PID regulator for
the CFL number. For Manual enter a Local CFL number CFLloc (dimensionless).

• Pseudo Time Stepping for Laminar Flow Models in this guide and
Pseudo Time Stepping in the COMSOL Multiphysics Reference
Manual
• Domain and Boundary Nodes for Bubbly Flow
• Theory for the Bubbly Flow Interface

THE BUBBLY FLOW INTERFACE | 457

 Domain and Boundary Nodes for Bubbly Flow
The following domain and boundary 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).

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.

DOMAIN
• Fluid Properties
• Volume Force (described for The Laminar Flow and Creeping Flow Interfaces)
• Mass Transfer
• Gravity
• Initial Values

BOUNDARY

The sections describe the available boundary conditions for the liquid and
the gas. In all equations, n denotes the outward pointing unit vector
normal to the boundary.

The boundary types for the liquid flow variables, described in this section, are:

• Wall (the default boundary condition)

• Inlet
• Outlet
• Symmetry
• Periodic Flow Condition
• Interior Wall

PAIR
• Flow Continuity

458 | CHAPTER 7: FLUID FLOW INTERFACES

In addition to the boundary conditions for the liquid, the following boundary
conditions for the gas are available for all boundary condition types except symmetry
and interior wall:

• Gas Concentration (the default condition for inlets)

• Gas Flux
• Gas Outlet (the default condition for outlets)
• No Gas Flux (the default condition for walls)
• Symmetry

Gas Boundary Condition Equations

For 2D 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.

Fluid Properties
The Fluid Properties node contains the material properties for the liquid and the gas. It
also contains settings for the slip model.

MODEL INPUTS
Fluid properties, such as the gas density and liquid 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 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.

THE BUBBLY FLOW INTERFACE | 459

 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 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

MATERIALS
Select the materials to use for the material properties of the liquid and the gas (when
they are set to take their value from the material). The default is to use the Domain
material for the Liquid and None for the Gas. Select another material to use that
material’s properties for the liquid or gas as needed.

LIQUID PROPERTIES
The default Density, liquid phase l (SI unit: kg/m3) uses values From material. For User
defined enter another value or expression.

The density in a material can depend on temperature and/or pressure and these
dependencies are automatically replaced by pref and Tref, which are specified at the
physics interface level.

The default Dynamic viscosity, liquid phase l (SI unit: Pa·s) uses values From material;
the value is then defined for the material selected in the Materials section for the
continuous phase. For User defined enter another value or expression.

460 | CHAPTER 7: FLUID FLOW INTERFACES

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.

GAS PROPERTIES
The default Density, gas phase g (SI unit: kg/m3) uses values From material. For User
defined enter another value or expression. Alternatively, select Calculate from ideal gas
law and enter the Molecular weight M (SI unit: kg/mol) of the gas.

Enter the Bubble diameter db (SI unit: m). The default value is 103 m (1 mm).

SLIP MODEL
Select a Slip model — Homogeneous flow (the default), Pressure-drag balance, or User
defined.

Homogeneous flow assumes that the velocity of the two phases are equal; that is,
uslip  0. For User defined enter different values or expressions for the components of
the Slip velocity uslip (SI unit: m/s).

For Pressure-drag balance it uses a model based on the assumption that the pressure
forces on a bubble are balanced by the drag force:

3 C
--- ------d-  l u slip u slip = – p
4 db

Here db (SI unit: m) is the bubble diameter, and Cd (dimensionless) is the drag
coefficient.

Select a Drag coefficient model:

• Small spherical bubbles (Hadamard-Rybczynski) for bubbles with a diameter smaller

than 2 mm.
• Large bubbles for gas bubbles with a diameter larger than 2 mm. Then enter the
Surface tension coefficient  (SI unit N/m). The default is 0.07 N/m.
• Air bubbles in tap water (Schwarz-Turner) for air bubbles of 1–10 mm mean diameter
in water.
User defined to enter a different value or expression for the Drag coefficient Cd
(dimensionless). The default value is 1.

THE BUBBLY FLOW INTERFACE | 461

 Mass Transfer
Add a Mass Transfer node to include mass transfer from the gas to the liquid.

MASS TRANSFER
Select a Mass transfer model — Two-film theory, Nonequilibrium model, or User defined.
For User defined enter a value or expression for the Mass transfer from gas to liquid mgl
(SI unit: kg/(m3·s)). The default is 0 kg/(m3·s).

Nonequilibrium Model
For Nonequilibrium model enter values or expressions for each of the following:

• Equilibrium volume fraction in dispersed phase  eq. The default is 0.

• Inverse time scales fl and fg (SI unit: 1/s). The default is 0 s-1.
The mass transfer is modeled as

m gl =  g  f l max   g –  eq  – f g max   eq –  g  

Two-film theory
For Two-film theory enter values for the Mass transfer coefficient k (SI unit: m/s),
Henry’s constant H (SI unit: Pa·m3/mol), the Dissolved gas concentration c (SI unit:
mol/m3), and the Molecular weight of species M (SI unit: kg/mol). Refer to the theory
below for more information.

Henry’s law gives the equilibrium concentration c* of gas dissolved in liquid:

p + p ref
c = -------------------
H

where H is Henry’s constant. The molar flux per interfacial area, N (SI unit: mol/
(s·m2)), is determined by

N = k  c – c 

where k is the Mass transfer coefficient and c is the Dissolved gas concentration in
liquid.

The mass transfer from gas to liquid, mgl, is given by

m gl = NMa

462 | CHAPTER 7: FLUID FLOW INTERFACES

where M is the Molecular weight of species and a is the interfacial area per volume
(SI unit: m2/m3).

Also see Theory for the Bubbly Flow Interface for details about how a is
computed.

For two-film theory, you also need to solve for the concentration of the dissolved gas;

c m gl
+    cu l  =    Dc  + ---------
t M

which can be done by adding a Transport of Diluted Species interface.

Gravity
The Gravity node adds the force g to the right-hand side of the momentum transport
equation. Gravity nodes are mutually exclusive, that is, there can only be one active
Gravity node per domain.

GRAVITY
Enter the components of the Gravity vector, g (SI unit: m/s2). For 2D components
the default Gravity vector is defined as 0g_const. Here g_const is a physical
constant equal to 9.8066 m/s2. For 3D and 2D axisymmetric components, the gravity
acts in the negative z direction by default.

Initial Values
The Initial Values node adds initial values for the flow variables and the effective gas
density that can serve as initial conditions for a transient simulation or as an initial guess
for a nonlinear solver.

INITIAL VALUES
Enter initial values or expressions for the Velocity field, liquid phase u (SI unit: m/s)
and for the Pressure p (SI unit: Pa). The default values are 0. Also enter a value or
expression for the Effective gas density rhogeff (SI unit: kg/m3). The default is 0 kg/
m3.

If the Solve for interfacial area check box is selected, enter an initial value for the Number
density, gas phase nd (SI unit: 1/m3). The default is 0 1/m3.

THE BUBBLY FLOW INTERFACE | 463

 Wall
The Wall node adds a selection of boundary conditions that describe the existence of a
solid wall. The Wall node by default specifies no gas flux for the gas phase.

Gas Boundary Condition Equations

LIQUID BOUNDARY CONDITION

Select a Liquid boundary condition — No slip (the default) or Slip.

No Slip
No slip is the default boundary condition for the liquid. A no slip wall is a wall where
the liquid velocity relative to the wall velocity is zero. For stationary walls, it sets the
liquid velocity to zero at the wall:

ul = 0

Slip
Sets the velocity component normal to the wall to zero:

ul  n = 0

GAS BOUNDARY CONDITION

From the list, select a Gas boundary condition for the gas phase on the wall — No gas
flux (the default), Gas concentration, Gas outlet, Gas flux, or Symmetry.

Gas Concentration
For Gas concentration enter the Effective gas density  g  g0 (SI unit: kg/m3). The
default is 0 kg/m3.If Solve for interfacial area is selected, also select either the Bubble
number density (the default) or the Bubble diameter and gas density button.

• For Bubble number density enter the Bubble number density n0 (SI unit: 1/m3). The
default is 1000 1/m3.
• For Bubble diameter and gas density enter the Bubble diameter db (SI unit: m) (the
default is 1 mm) and Density, gas phase g (SI unit: kg/m3) (the default is 1 kg/
m3).

464 | CHAPTER 7: FLUID FLOW INTERFACES

Gas Flux
For Gas flux enter the Gas mass flux N  g  g (SI unit: kg/(m2·s)) (the default is 0 kg/
(m2·s)) and if the Solve for interfacial area check box is selected on the physics interface,
the Number density flux Nn (SI unit: 1/(m2·s)). The default is 0 (1/(m2·s)).

WALL MOVEMENT
This section contains controls to describe the wall movement relative to the spatial
frame.

The Translational velocity setting controls the translational velocity, utr. The list is per
default set to Automatic from frame. When Automatic from frame is selected, the physics
automatically detects if the spatial frame moves. If there is no movement, utr is set to
0. If the frame moves, utr becomes equal to the frame movement. utr is accounted for
in the actual boundary condition prescribed in the Liquid boundary condition section.

When Manual is selected from Translational velocity selection list, the Velocity of moving
wall, utr can be prescribed manually. Specifying the translational velocity manually
does not automatically cause the associated wall to move. An additional Moving Mesh
interface needs to be added to physically track the wall movement in the spatial
reference frame.

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

CONSTRAINT SETTINGS
This section is displayed by clicking the Show More Options button ( ) and selecting
Advanced Physics Options.

Wall in the Single-Phase Flow interfaces

THE BUBBLY FLOW INTERFACE | 465

 Inlet
The Inlet node adds a selection of boundary conditions that describe inlets in fluid-flow
simulations.

Gas Boundary Condition Equations

LIQUID BOUNDARY CONDITION

Select a Liquid boundary condition — Velocity (the default), Pressure, or Fully developed
flow.

VELOCITY
For Velocity click the Normal inflow velocity (the default) or Velocity field buttons.

• For Normal inflow velocity enter a value or expression for U0 (SI unit: m/s).
• For Velocity field specify that the velocity at the boundary is equal to a given u0 (SI
unit: m/s) and enter the components in the matrix:
ul = u0

PRESSURE
This condition specifies the normal stress which in most cases is approximately equal
to the pressure. Enter the Pressure p0 (SI unit: Pa) at the boundary. The default is 0 Pa.
Enter a relative pressure value in p0 (SI unit: Pa). Or if the reference pressure pref
defined at the physics interface level is equal to 0 Pa, enter an absolute pressure in p0.

• The Suppress backflow check box is selected by default. This option adjusts the inlet
pressure, pˆ 0  p 0 , locally in order to reduce the amount of fluid exiting the domain
through the boundary. If suppress backflow is deselected, the inlet boundary can
become an outlet depending on the pressure field in the rest of the domain.
• Flow direction controls in which direction the fluid enters the domain.
- For Normal flow (the default) it prescribes zero tangential velocity component.
- For User defined define an Inflow velocity direction, du (dimensionless). The
magnitude of du does not matter, only the direction. du must point into the
domain.

466 | CHAPTER 7: FLUID FLOW INTERFACES

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 velocity is defined by
the boundary condition of the adjacent boundary in the model.

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).

Select a Fully developed flow option — Average velocity (the default), Flow rate, or
Average pressure.

The Fully developed flow option adds contributions to the inflow boundary, which force
the flow toward the solution for a fully developed channel flow.

Select an option to control the flow rate at the inlet:

• For Average velocity enter 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 inflow
boundary.

Fully developed inflow can be used in conjunction with the turbulence models. No
additional inputs are required for the turbulence variables. They are instead solved for
on the inlet boundary to be consistent with the fully developed flow profile.

A fully developed flow boundary cannot be adjacent to any Interior Wall feature

GAS BOUNDARY CONDITION

These settings are the same as for Wall. See Gas Boundary Condition. The only
difference is that Gas concentration is the default.

Outlet
The Outlet node adds a set of boundary conditions that describe outlets in fluid-flow
simulations; that is, the conditions at boundaries where the fluid exits the domain.

THE BUBBLY FLOW INTERFACE | 467

 LIQUID BOUNDARY CONDITION
Select a Liquid boundary condition — Pressure (the default), Velocity, or Fully developed
flow.

PRESSURE CONDITIONS
The Pressure condition specifies the normal stress which in most cases is approximately
equal to the pressure. The tangential stress component is set to 0 N/m2.

• Enter the Pressure p0 (SI unit: Pa) at the boundary. The default is 0 Pa. Enter a
relative pressure value in p0 (SI unit: Pa). Or if the reference pressure pref defined
at the physics interface level is equal to 0 Pa, enter an absolute pressure in p0.
• Select the Normal flow check box to change 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
For Velocity click the Velocity field (the default) or Normal outflow velocity buttons.

• For Velocity field specify that the velocity at the boundary is equal to a given u0 (SI
unit: m/s) and enter the components in the matrix:
ul = u0

• For Normal outflow velocity enter a value or expression for U0 (SI unit: m/s).

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 boundary conditions for the virtual inlet 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).

Select a Fully developed flow option — Average velocity (the default), Flow rate, or
Average pressure.

468 | CHAPTER 7: FLUID FLOW INTERFACES

GAS BOUNDARY CONDITION
The settings for the Gas boundary condition are the same as for Wall. See Gas Boundary
Condition.

When the Gas boundary condition is set to Gas outlet, the Exterior gas condition(s)
section contains an input field for the Effective gas density on the downstream side of
the outlet. If Solve for interfacial area is selected at the physics interface level, additional
input fields appear for the Bubble number density or the Bubble diameter and gas density
on the downstream side of the outlet.

See in the Single-Phase Flow interfaces

Symmetry
The Symmetry node adds boundary conditions that describe symmetry boundaries in
fluid-flow simulations. The boundary condition for symmetry boundaries prescribes
no penetration and vanishing shear stresses:

t T   l   l +  T   u l + u l – ---    u l I  n = 0
T 2
u l  n = 0,
  3 

BOUNDARY SELECTION
A boundary condition for 2D axial symmetry is not required.

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 is valid on the axial symmetry boundaries only.

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 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 ).

THE BUBBLY FLOW INTERFACE | 469

 PRESSURE DIFFERENCE
A value or expression should be specified for the Pressure difference, psrc  pdst. 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 More Options button ( ) and selecting
Advanced Physics Options in the Show More Options dialog box.

ORIENTATION OF SOURCE
For information about the Orientation of Source section, see Orientation of Source and
Destination in the COMSOL Multiphysics Reference Manual.

Interior Wall
The Interior Wall node adds a wall boundary condition on interior boundaries. It is
similar to the Wall boundary condition available on exterior boundaries except that it
applies on both sides of an interior boundary. It allows discontinuities of the dependent
variables across the boundary. The Interior Wall node specifies no gas flux for the gas
phase.

Gas Boundary Condition Equations

LIQUID BOUNDARY CONDITION

Select a Liquid boundary condition — No slip (the default) or Slip.

No Slip
No slip is the default boundary condition for the liquid. A no slip wall is a wall where
the liquid velocity relative to the wall velocity is zero. For interior stationary walls, it
sets the liquid velocity to zero on both sides of the wall:

ul = 0

470 | CHAPTER 7: FLUID FLOW INTERFACES

For turbulent bubbly flows, the no slip condition may either be prescribed exactly or
modeled using automatic wall treatment or wall functions depending on the Wall
Treatment setting in the Turbulence section of the interface settings.

Slip
The Slip condition prescribes a no-penetration condition. For an interior stationary
wall it sets the velocity component normal to the interior wall to zero on both sides of
the wall:

ul  n = 0

WALL MOVEMENT
This section contains controls to describe the wall movement relative to the spatial
frame.

The Translational velocity setting controls the translational velocity, utr. The list is per
default set to Automatic from frame. When Automatic from frame is selected, the physics
automatically detects if the spatial frame moves. If there is no movement, utr is set to
0. If the frame moves, utr becomes equal to the frame movement. utr is accounted for
in the actual boundary condition prescribed in the Liquid boundary condition section.

When Manual is selected from Translational velocity selection list, the Velocity of moving
wall, utr can be prescribed manually. Specifying the translational velocity manually
does not automatically cause the associated wall to move. An additional Moving Mesh
interface needs to be added to physically track the wall movement in the spatial
reference frame.

CONSTRAINT SETTINGS
This section is displayed by clicking the Show More Options button ( ) and selecting
Advanced Physics Options.

Wall

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.

THE BUBBLY FLOW INTERFACE | 471

 A Wall subnode is added by default and it applies to the parts of the pair boundaries
where a source boundary lacks a corresponding destination boundary and vice versa.
The Wall feature can be overridden by any other boundary condition that applies to
exterior boundaries. By right-clicking the Flow Continuity node, additional Fallback
feature subnodes can be added.

Gas Boundary Condition Equations

In addition to the boundary conditions for the liquid, specify boundary conditions for
the gas on Wall, Inlet, Outlet, and Interior Wall nodes. Select a Gas Boundary Condition:

Gas Concentration
Using this boundary condition, specify the effective gas density.

0
̃ g = ̃ g

Gas Outlet
This boundary condition is appropriate for boundaries where the gas phase flows
outward with the gas velocity, ug, at the boundary.

Gas Flux
Using this boundary condition, specify the gas mass flux through the boundary:

– n   ̃ g u g  = N g  g

Symmetry
This boundary condition, which is useful on boundaries that represent a symmetry line
for the gas flow, sets the gas flux through the boundary to zero:

n   ̃ g u g  = 0

No Gas Flux
This boundary condition represents boundaries where the gas flux through the
boundary is zero:

n   g ug  = 0

In walls moving with a boundary velocity u bnd , the gas flux through the boundary is:

n    g u g  = n    g u bnd 

472 | CHAPTER 7: FLUID FLOW INTERFACES

The Mixture Model Interface
In this section:

• The Mixture Model, Laminar Flow Interface

• Domain and Boundary Nodes for the Mixture Model Interface

The Mixture Model, Laminar Flow Interface

The Mixture Model, Laminar Flow (mm) interface ( ), found under the Multiphase
Flow>Mixture Model branch ( ) when adding a physics interface, is used to model the
flow at low and moderate Reynolds numbers of liquids containing a dispersed phase.
The dispersed phase can be bubbles, liquid droplets, or solid particles, which are
assumed to always travel with their terminal velocity.

The Mixture Model, Laminar Flow interface solves one set of Navier–Stokes equations
for the momentum of the mixture. The pressure distribution is calculated from a
mixture-averaged continuity equation and the velocity of the dispersed phase is
described by a slip model. The volume fraction of the dispersed phase is tracked by
solving a transport equation for the volume fraction.

The physics interface can also model the distribution of the number density, which in
turn can be used to calculate the interfacial area, which is useful when simulating
chemical reactions in the mixture.

The main physics node is the Mixture Properties feature, which adds the equations for
the mixture and provides an interface for defining the fluid materials for the
continuous and dispersed phases as well as which slip model and mixture viscosity
model to use.

When this physics interface is added, the following default physics nodes are also added
in the Model Builder — Mixture Properties, Wall, 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 Mixture Model, Laminar Flow to select
physics features from the context menu.

SETTINGS
The Label is the default physics interface name.

THE MIXTURE MODEL INTERFACE | 473

 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 mm.

PHYSICAL MODEL
Specify the characteristics of the dispersed phase, the model for the slip velocity, and
whether or not to solve for the interfacial area.

Dispersed Phase
To characterize the Dispersed phase, select Solid particles (the default) or Liquid
droplets/bubbles.

The selection from this list is further defined for the Mixture Properties node under
the Mixture Model section.

Slip Model
To compute the slip velocity jslip (SI unit: m/s), select a Slip model — Homogeneous
flow (the default), Hadamard-Rybczynski, Schiller-Naumann, Haider-Levenspiel, or User
defined.

• The Homogeneous flow model assumes that the velocities of the two phases are equal,
that is, uslip = 0.
• In most cases there is a significant difference in the velocity fields due to the
buoyancy of the dispersed phase. Use one of the predefined slip models for such
cases.
• For User defined specify an arbitrary expression for the relative velocity. For example,
give a constant velocity based on experimental data. Enter the Slip velocity field uslip
(SI unit: m/s) or Slip flux jslip (SI unit: m/s) in the Mixture Properties node under
the Mixture Model section.

Solve For Interfacial Area

To add a transport equation for the number density of the dispersed particles, in order
to determine the interfacial area, select the Solve for interfacial area check box (by
default not selected).

For the Mass Transfer rate, use a two-film theory model, which includes the interfacial
area per unit volume between the two phases. It is possible to compute the interfacial

474 | CHAPTER 7: FLUID FLOW INTERFACES

area per unit volume if the number density n (that is, the number of dispersed particles
per volume) is known. Select the Solve for interfacial area check box to add the
following equation for the number density n:

n
+ j  n +    nu slip  c  = 0
t

This equation states that a dispersed phase particle cannot disappear, appear, or merge
with other particles, although it can expand or shrink.

The Mixture Model, Laminar Flow Interface calculates the interfacial area a
(SI unit: m2/m3) from

13 23
a =  4n   3 d 

Reference values
Reference values are global quantities used to evaluate the density of both phases and
the absolute pressure pA.

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 density of both phases. The default Reference
pressure level pref (SI unit: Pa) is 1[atm].

Reference temperature The reference temperature is used to define the density of

both phases. The default Reference temperature Tref (SI unit: K) is 293.15[K].

Swirl Flow
For 2D axisymmetric components, select the Swirl flow check box to include the swirl
velocity component — that is, the velocity component j  in the azimuthal direction.
While j  can be nonzero, there can be no gradients in the  direction

General Single-Phase Flow Theory

THE MIXTURE MODEL INTERFACE | 475

 DEPENDENT VARIABLES
Enter values for the dependent variables (field variables):

• Velocity field, mixture j (SI unit: m/s)

• Pressure p (SI unit: Pa)
• Volume fraction, dispersed phase phid (dimensionless)
• Squared slip velocity slipvel
• Number density, dispersed phase nd (SI unit: 1/m3).

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

CONSISTENT STABILIZATION AND INCONSISTENT STABILIZATION

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

The consistent stabilizations Streamline diffusion and Crosswind diffusion are by default
applied to the Navier-Stokes and dispersed phase transport equations. In addition, when
the flow is turbulent, the consistent stabilizations are also applied to the Turbulence.
Additional inconsistent stabilization terms may be added when required as isotropic
diffusion.

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.

Penalty Diffusion can be used to suppress negative values of the dispersed volume
fraction. Including this term has been observed to slow down convergence and it is
therefore disabled by default.

Select the Use pseudo time stepping for stationary equation form check box to add
pseudo time derivatives to the equation when the Stationary equation form is used.
When selected, also choose a CFL number expression — Automatic (the default) or
Manual. Automatic sets the local CFL number (from the Courant–Friedrichs–Lewy

476 | CHAPTER 7: FLUID FLOW INTERFACES

condition) to the built-in variable CFLCMP which in turn triggers a PID regulator for
the CFL number. For Manual enter a Local CFL number CFLloc (dimensionless).

• Pseudo Time Stepping for Laminar Flow Models in this guide and
Pseudo Time Stepping in the COMSOL Multiphysics Reference
Manual
• Domain and Boundary Nodes for the Mixture Model Interface
• Slip Velocity Models and Theory for the Mixture Model Interface

Polymer Electrolyte Membrane Electrolyzer: Application Library path

Fuel_Cell_and_Electrolyzer_Module/Electrolyzers/pem_electrolyzer

Domain and Boundary Nodes for the Mixture Model Interface

The following domain and boundary 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).

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.

DOMAIN
• Mixture Properties
• Mass Transfer
• Volume Force (described for The Laminar Flow Interface)
• Gravity
• Initial Values

BOUNDARY
The boundary types for the mixture flow variables, described in this section, are:

• Wall (the default boundary condition feature)

• Inlet
• Outlet

THE MIXTURE MODEL INTERFACE | 477

 • Symmetry
• Periodic Flow Condition
• Interior Wall

PAIR
• Mixture Continuity
For the flow variables, the velocity and the pressure, the boundary conditions
correspond to those defined for single phase flow (see ). There is also a point constraint
for the pressure, which is useful if no other boundary condition in the model includes
a pressure level constraint.

The following boundary conditions for the dispersed phase are available for all
boundary condition types except symmetry and interior wall. These are described in
more detail in the .

• Dispersed phase concentration (the default condition for inlets)

• Dispersed phase flux
• Dispersed phase outlet (the default condition for outlets)
• No dispersed phase flux (the default condition for walls)
• Symmetry

For 2D 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.

Mixture Properties
The Mixture Properties node contains the material properties for the continuous phase
and the dispersed phase. It also contains settings for the viscosity model. For the
Mixture Model, Turbulent Flow interfaces, the Mixture Properties node also adds the
equations for the turbulence transport equations.

MODEL INPUTS
The viscosity of each phase 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.

478 | CHAPTER 7: FLUID FLOW INTERFACES

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 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

MATERIALS
Select the fluid materials to use for the material properties. The default material used
for the Continuous phase is the Domain material. This corresponds to the material
currently applied to the domain in question. The Dispersed phase uses None per default.
A valid material must be selected instead.

THE MIXTURE MODEL INTERFACE | 479

 CONTINUOUS PHASE PROPERTIES
The default Density, continuous phase c (SI unit: kg/m3) uses values From material (as
selected in the Materials section). For User defined enter another value or expression. In
this case the default is 0 kg/m3.

The density in a material can depend on temperature and/or pressure and these
dependencies are automatically replaced by pref and Tref, which are specified at the
physics interface level.

The default Dynamic viscosity, continuous phase c (SI unit: Pa·s), uses values From
material. It 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. For User defined enter another value or
expression. In this case, the default is 0 Pa·s.

DISPERSED PHASE PROPERTIES

The default Density, dispersed phase d (SI unit: kg/m3) uses values From material (as
selected in the Materials section). For User defined enter another value or expression. In
this case, the default is 0 kg/m3.

The density in a material can depend on temperature and/or pressure and these
dependencies are automatically replaced by pref and Tref, which are specified at the
physics interface level.

Enter the Diameter of particles/droplets dd (SI unit: m). The default is 103 m (1 mm).
If Haider-Levenspiel is selected for the Slip model under Physical Model, enter a value
between 0 and 1 for the Sphericity (dimensionless). The default is 1.

If Liquid droplets/bubbles is selected from the Dispersed phase list in the interface, then
Dynamic viscosity, dispersed phase d (SI unit: Pa·s) is also available. The default uses
values From material (as selected in the Materials section) or select User defined to enter
another value or expression. In this case, the default is 0 Pa·s.

MIXTURE MODEL
The options in this section are based on the selection made from the Dispersed phase
list for the Mixture Model interfaces.

480 | CHAPTER 7: FLUID FLOW INTERFACES

Slip Velocity Field
When a User defined Slip model is selected for the physics interface, specify an arbitrary
expression for the relative velocity. For example, give a constant velocity based on
experimental data.

• When Slip velocity is set to Specify slip velocity field, enter the slip velocity between
the two phases, uslip (SI unit: m/s).
• When Slip velocity is set to Specify slip flux, enter the slip flux jslip (SI unit: m/s).

• The Mixture Model Equations in Theory for the Mixture Model

Interface

Mixture Viscosity Model

Select the Mixture viscosity model.

• When Solid particles is the Dispersed phase, select either Krieger type (the default) or
User defined.
• When Liquid droplets/bubbles is the Dispersed phase, select Krieger type (the default),
User defined, or Volume averaged.

For User defined enter a value or expression for the Dynamic viscosity  (SI unit: Pas).
The default is 0 Pas. When using this option, make sure to limit the viscosity to
bounded positive values.

When Krieger type is selected, enter a value or expression for the Maximum packing
concentration  max (dimensionless). The default is 0.62.

Select Krieger type to model the most generally valid expression for the mixture
viscosity:

 d – 2.5 max 
 =  c  1 – ------------
  max

where  max is the maximum packing concentration, which for solid particles is
approximately 0.62. The dimensionless parameter *  1 for solid particles and

 d + 0.4 c
 = ---------------------------
d + c

for droplets and bubbles. When applying the Krieger type viscosity model, d is
replaced by min(  d , 0.999  max ) for better robustness.

THE MIXTURE MODEL INTERFACE | 481

 Select Volume averaged to model the mixture viscosity of liquid-liquid mixtures, which
uses the following equation for the viscosity:

 = d d + c c

The Mixture Model interfaces always employ the mixture viscosity in the particle
Reynolds number expression used to calculate the slip velocity, thereby accounting for
the increase in viscous drag due to particle-particle interactions.

Mass Transfer
Use the Mass Transfer node to include mass transfer from the dispersed phase to the
continuous phase.

MASS TRANSFER
Select a Mass transfer model — User defined (the default), Nonequilibrium model, or
Two-film theory. For User defined enter a value or expression for the Mass transfer from
dispersed to continuous phase mdc (SI unit: kg/(m3·s)). The default is 0 kg/(m3·s).

Nonequilibrium Model
For Nonequilibrium model enter values or expressions for each of the following:

• Equilibrium volume fraction in dispersed phase  eq. The default is 0.

• Inverse time scales fc and fd (SI unit: 1/s). The default is 0 s-1.
The mass transfer is modeled as

m dc =  d  max  f c   d –  eq  0  – max  f d   eq –  d  0  

Two-Film Theory
For Two-film theory enter values or expressions for each of the following:

• Mass transfer coefficient k (SI unit: m/s). The default is 0 m/s.

• Species concentration in dispersed phase cd (SI unit: mol/m3). The default is 0 mol/
m3 .
• Species concentration in continuous phase cc (SI unit: mol/m3). The default is
0 mol/m3.
• Molecular weight of species M (SI unit: kg/mol). The default is 0 kg/mol.

The mass transfer is modeled as

m dc = k  c d – c c Ma

482 | CHAPTER 7: FLUID FLOW INTERFACES

where k denotes the mass transfer rate, and cd and cc are the species concentrations in
the dispersed and the continuous phase, respectively. M is the species’ molecular
weight, and a is the interfacial area per unit volume between the two phases. The Mass
transfer model — Two-film theory is available when the Solve for interfacial area check
box is selected (under the Physical Model section).

Gravity
The Gravity node adds the force g to the right-hand side of the momentum transport
equation.

GRAVITY
Enter the components of the Gravity vector, g (SI unit: m/s2). The default value is
(0,-g_const) where g_const is a physical constant equal to 9.8066 m/s2.

For 2D components, gravity acts in the negative y direction by default.

For example, in a 2D component, the y component is -g_const and the
other component is 0. In this setting, g_const is a predefined physical
constant for the standard gravity (acceleration due to gravity at sea level).

For 3D and 2D axisymmetric components, gravity acts in the negative z

direction by default. For example, in a 3D component, the z component
is -g_const and the other components are 0. In this setting, g_const is
a predefined physical constant for the standard gravity (acceleration due
to gravity at sea level).

Initial Values
The Initial Values node adds initial values for the mixture velocity, pressure, and volume
fraction of the dispersed phase, that can serve as an initial condition for a transient
simulation or as an initial guess for a nonlinear solver.

INITIAL VALUES
Enter values or expressions for the following dependent variables:

• Velocity field, mixture, the components of j (SI unit: m/s). The defaults are 0 m/s.
• Pressure p (SI unit: Pa). The default is 0 Pa.

THE MIXTURE MODEL INTERFACE | 483

 • Volume fraction, dispersed phase (dimensionless). The default is 0.
• If the Solve for interfacial area check box is selected for the physics interface, enter
an initial value for the Number density, dispersed phase nd (SI unit: 1/m3). The
default is 0 1/m3.
• If a Schiller-Naumann or a Haider-Levenspiel slip model is used in the physics interface,
enter an initial value for the Squared slip velocity slipvel (SI unit: m2/s2). The
default is 0.081 m2/s2.

For the Mixture Model, Turbulent Flow interfaces, initial values for the turbulence
variables should be also specified. Additional initial values may be required for:

• Turbulent kinetic energy k

• Turbulent dissipation rate ep
• Reciprocal wall distance G
• Specific dissipation rate om
• Undamped turbulent kinematic viscosity 0
• Wall distance in viscous units yPlus
• Tangential velocity in viscous units uPlus
• Turbulent relative fluctuations zeta
• Elliptic blending function alpha

The following sections describe the available boundary conditions for the
mixture and the dispersed phase volume fraction. In all equations, n
denotes the outward pointing unit vector normal to the boundary.

Wall
The Wall node has boundary conditions available that describe the existence of a solid
wall.

484 | CHAPTER 7: FLUID FLOW INTERFACES

MIXTURE BOUNDARY CONDITION
Select a Mixture boundary condition for the wall.

• No Slip
• Slip
• Navier Slip

No Slip
No slip is the default boundary condition for the liquid. A no slip wall is a wall where
the mixture velocity relative to the wall velocity is zero. For stationary walls, it sets the
mixture velocity to zero at the wall:

j = 0

Slip
Select Slip to set the velocity component normal to the wall to zero j  n wall = 0 .

Navier Slip
This boundary condition enforces no-penetration at the wall, j  n wall = 0 , and adds
a friction force of the form


F fr = – --- j tan g


where is a slip length, and j tan g = j –  j  n wall n wall is the velocity tangential to the
wall. The boundary condition does not set the tangential velocity component to zero;
however, the extrapolated tangential velocity component is 0 at a distance  outside of
the wall. In cases where the wall movement in non-zero, check Account for the
translational wall velocity in the friction force to use
 j – u bnd –   j – u bnd   n wall n wall  instead of jtang in the friction force. Then, the
extrapolated tangential velocity component is ubnd at a distance  outside of the wall.
Note that the Velocity of sliding wall uw is always accounted for in the friction force.

The Navier Slip boundary condition is suitable for walls adjacent to a free surface when
solving for laminar flow. Applying this boundary condition, the contact line
(fluid-fluid-solid interface) is free to move along the wall. Note that in problems with
contact lines, the tangential velocity of the wall typically represents the movement of
the contact line but the physical wall is not moving. In such cases, Account for the
translational wall velocity in the friction force should not be selected.

THE MIXTURE MODEL INTERFACE | 485

 The Slip length setting is per default set to Factor of minimum element length. The slip
length  is then defined as   fhhmin, where hmin is the smallest element side
(corresponds to the element size in the wall normal direction for boundary layer
elements) and fh is a user input. Select User defined from the Slip length list to manually
prescribe 

DISPERSED PHASE BOUNDARY CONDITION

Select a Dispersed phase boundary condition — No dispersed phase flux (the default),
Dispersed phase concentration, Dispersed phase outlet, Dispersed phase flux, or Symmetry.

• For Dispersed phase concentration enter a Dispersed phase volume fraction  d0

(dimensionless). The default is 0. When Solve for interfacial area is selected under
the Physical Model section, click either the Dispersed phase number density n0
(SI unit: 1/m3) or Diameter of particles/droplets dd (SI unit: m) button and enter a
value or expression for n0 (the default is 5·106 1/m3) or dd (the default is 1 mm).
• For Dispersed phase flux enter values or expression for the Dispersed phase flux N d
(SI unit: m/s) and, if Solve for interfacial area is selected under the Physical Model
section, the Number density flux n (SI unit: 1/(m2s)). The defaults are 0 m/s and
0 1/(m2s), respectively.

Dispersed Phase Boundary Condition Equations

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 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

486 | CHAPTER 7: FLUID FLOW INTERFACES

associated wall to move. An additional Moving Mesh interface needs to be added 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; that is,
the surface is sliding in its 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.

Wall in the Single-Phase Flow interfaces

Inlet
The Inlet node adds a set of boundary conditions that describe inlets in fluid-flow
simulations.

MIXTURE BOUNDARY CONDITION

Select a Mixture boundary condition for the inlet — Velocity (the default) or Pressure.

VELOCITY
For Velocity click the Normal inflow velocity (the default) or Velocity field buttons.

• For Normal inflow velocity enter a value or expression for J0 (SI unit: m/s).
• For Velocity field specify that the velocity at the boundary is equal to a given j0 (SI
unit: m/s) and enter the components in the matrix:
j = j0

THE MIXTURE MODEL INTERFACE | 487

 PRESSURE
This condition specifies the normal stress which in most cases is approximately equal
to the pressure. Enter the Pressure p0 (SI unit: Pa) at the boundary. The default is 0 Pa.
Enter a relative pressure value in p0 (SI unit: Pa). Or if the reference pressure pref
defined at the physics interface level is equal to 0 Pa, enter an absolute pressure in p0.

• The Suppress backflow check box is selected by default. This option adjusts the inlet
pressure, pˆ 0  p 0 , locally in order to reduce the amount of fluid exiting the domain
through the boundary. If suppress backflow is deselected, the inlet boundary can
become an outlet depending on the pressure field in the rest of the domain.
• Flow direction controls in which direction the fluid enters the domain.
- For Normal flow (the default) it prescribes zero tangential velocity component.
- For User defined define an Inflow velocity direction, dj (dimensionless). The
magnitude of dj does not matter, only the direction. dj must point into the
domain.

DISPERSED PHASE BOUNDARY CONDITION

The default is Dispersed phase concentration. See Wall>Dispersed Phase Boundary
Condition for the settings.

See Dispersed Phase Boundary Condition Equations for more information.

See Inlet in the Single-Phase Flow interfaces

Outlet
The Outlet node adds a selection of boundary conditions that describe outlets in
fluid-flow simulations; that is, the conditions at boundaries where the fluid exits the
domain.

MIXTURE BOUNDARY CONDITION

Select a Mixture boundary condition for the outlet — Pressure (the default) or Velocity.

488 | CHAPTER 7: FLUID FLOW INTERFACES

PRESSURE CONDITIONS
The Pressure condition specifies the normal stress which in most cases is approximately
equal to the pressure. The tangential stress component is set to 0 N/m2.

• Enter the Pressure p0 (SI unit: Pa) at the boundary. The default is 0 Pa. Enter a
relative pressure value in p0 (SI unit: Pa). Or if the reference pressure pref defined
at the physics interface level is equal to 0 Pa, enter an absolute pressure in p0.
• Select the Normal flow check box to change 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
For Velocity click the Normal outflow velocity (the default) or Velocity field buttons.

• For Normal outflow velocity enter a value or expression for J0 (SI unit: m/s).
• For Velocity field specify that the velocity at the boundary is equal to a given j0 (SI
unit: m/s) and enter the components in the matrix:
j = j0

DISPERSED PHASE BOUNDARY CONDITION

The default is Dispersed phase outlet. See Wall>Dispersed Phase Boundary Condition
for the settings.

When the Dispersed phase boundary condition is set to Dispersed phase outlet, the
Exterior dispersed phase condition(s) section contains an input field for the Dispersed
phase volume fraction on the downstream side of the outlet. If Solve for interfacial area
is selected at the physics interface level, additional input fields appear for the Dispersed
phase number density or the Diameter of particles/droplets on the downstream side of
the outlet.

See Dispersed Phase Boundary Condition Equations for more information.

See Outlet in the Single-Phase Flow interfaces

THE MIXTURE MODEL INTERFACE | 489

 Symmetry
The Symmetry node adds boundary conditions that describe symmetry boundaries in
fluid-flow simulations. The boundary condition for symmetry boundaries prescribes
no penetration and vanishing tangential stress:

T
j  n = 0, t T    c +  d –  u slip j slip +  Gm n = 0

BOUNDARY SELECTION
A boundary condition for 2D axial symmetry is not required.

For the symmetry axis at r  0, the program automatically provides a condition that
prescribes ur  0 and vanishing stresses in the z direction and adds an Axial Symmetry
node that is valid on the axial symmetry boundaries only.

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 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).

PRESSURE DIFFERENCE
A value or expression should be specified for the Pressure difference, psrc  pdst. 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 More Options button ( ) and selecting
Advanced Physics Options.

490 | CHAPTER 7: FLUID FLOW INTERFACES

ORIENTATION OF SOURCE
For information about the Orientation of Source section, see Orientation of Source and
Destination in the COMSOL Multiphysics Reference Manual.

Interior Wall
The Interior Wall node adds a wall boundary condition on interior boundaries. It is
similar to the Wall boundary condition available on exterior boundaries except that it
applies on both sides of an interior boundary. It allows discontinuities of the dependent
variables across the boundary. The Interior Wall node specifies no flux for the dispersed
phase.

Dispersed Phase Boundary Condition Equations

MIXTURE BOUNDARY CONDITION

Select a Mixture boundary condition — No slip (the default), or Slip.

No Slip
No slip is the default boundary condition for the mixture. A no slip wall is a wall where
the mixture velocity relative to the wall velocity is zero. For a interior stationary wall,
it sets the mixture velocity to zero at the wall:

j = 0

Slip
Select Slip to set the velocity component normal to the wall to zero j  n = 0 .

Navier Slip
The Navier slip condition enforces no-penetration at the wall, j  n = 0 , and adds a
friction force of the form


F fr = – --- j


where is a slip length. For more information, see the Navier Slip option in the Wall
feature.

THE MIXTURE MODEL INTERFACE | 491

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

CONSTRAINT SETTINGS
This section is displayed by clicking the Show More Options button ( ) and selecting
Advanced Physics Options.

Wall

Mixture Continuity
The Mixture Continuity condition is suitable for pairs where the boundaries match; it
prescribes that the flow field is continuous across the pair.

A Wall subnode is added by default and it applies to the parts of the pair boundaries
where a source boundary lacks a corresponding destination boundary and vice versa.
The Wall feature can be overridden by any other boundary condition that applies to
exterior boundaries. By right-clicking the Mixture Continuity node, additional Fallback
feature subnodes can be added.

492 | CHAPTER 7: FLUID FLOW INTERFACES

The Euler-Euler Model Interface
In this section:

• The Euler-Euler Model, Laminar Flow Interface

• Domain, Boundary, Point, and Pair Nodes for the Euler–Euler Model Interfaces

The Euler-Euler Model, Laminar Flow Interface

The Euler-Euler Model, Laminar Flow (ee) interface ( ), found under the Multiphase
Flow>Euler-Euler Model branch ( ) when adding a physics interface, can be used to
simulate the flow of two continuous and fully interpenetrating incompressible phases
(see Ref. 1 under the Theory for the Euler-Euler Model Interfaces). The physics
interface can model flow at low and moderate Reynolds numbers. Typical applications
are fluidized beds (solid particles in gas), sedimentation (solid particles in liquid), or
transport of liquid droplets or bubbles in a liquid.

The physics interface solves two sets of Navier-Stokes equations, one for each phase,
in order to calculate the velocity field for each phase. The phases interchange
momentum as described by a drag model. The pressure is calculated from a
mixture-averaged continuity equation and the volume fraction of the dispersed phase
is tracked with a transport equation.

When this physics interface is added, the following default physics nodes are also added
in the Model Builder — Phase Properties, Wall, 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 Euler-Euler Model, Laminar 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 ee.

THE EULER-EULER MODEL INTERFACE | 493

 DISPERSED PHASE
Select a Dispersed phase — Solid particles or Liquid droplets/bubbles.

When Solid particles is selected, the section is available in the Phase Properties node.
Also see Dispersed Phase in the theory section.

PHYSICAL MODEL

Dispersed Phase
Select a Dispersed phase — Solid particles or Liquid droplets/bubbles.

When Solid particles is selected, the section is available in the Phase Properties node.
Also see Dispersed Phase in the theory section.

Reference Values
Reference values are global quantities used to evaluate the density of the fluid and
define the absolute pressure.

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 density of incompressible fluids.

Reference temperature The reference temperature is used to define the reference

density.

DEPENDENT VARIABLES
The dependent variables (field variables) are:

• Velocity field, continuous phase uc

• Velocity field, dispersed phase ud
• Pressure p
• Volume fraction, dispersed phase phid

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

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

494 | CHAPTER 7: FLUID FLOW INTERFACES

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

Inconsistent stabilization can be activated independently for the momentum equation

for the continuous phase, the momentum equation for the dispersed phase, and for the
dispersed phase transport equation respectively by selecting the corresponding check
box. Each inconsistent stabilization contribution has a tuning parameter.

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 Residue volume fraction, continuous phase,  c,res, and Residue volume fraction,
dispersed phase,  d,res, set the smallest values used to avoid division by zero when
evaluating terms that involve 1  c and 1  d. Observe that this value does not prevent
 c or  d from becoming smaller than  c,res and  d,res, respectively.

Select the Use pseudo time stepping for stationary equation form check box to add
pseudo time derivatives to the equation when the Stationary equation form is used.
When selected, also choose a CFL number expression — Automatic (the default) or
Manual. Automatic sets the local CFL number (from the Courant–Friedrichs–Lewy
condition) to the built-in variable CFLCMP which in turn triggers a PID regulator for
the CFL number. For Manual enter a Local CFL number CFLloc (dimensionless).

DISCRETIZATION
The Euler-Euler Model, Laminar Flow interface supports three options for the basis
functions: P1+P1 (the default option), P2+P1, and P3+P2. They all represent
Lagrangian basis functions of different orders:

• P1+P1 – Linear basis functions for all degrees of freedom. Linear basis functions are
computationally less expensive than the higher-order options and are also more
robust. This option requires that Streamline diffusion is activated for both of the
momentum equations.
• P2+P1 – Quadratic basis functions for all degrees of freedom except the pressure
which is described by linear basis functions. Higher order elements, as compared to
linear elements, are a computationally effective way to obtain high accuracy but only

THE EULER-EULER MODEL INTERFACE | 495

 if the flow is well resolved. This requirement is most likely fulfilled for flows with
very low velocities and/or small length scales.
• P3+P2 – Cubic basis functions for all degrees of freedom except the pressure which
is described by quadratic basis functions. This option is computationally very
expensive and the least robust one but it is also the option with the highest formal
accuracy.

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

• Pseudo Time Stepping for Laminar Flow Models in this guide and
Pseudo Time Stepping in the COMSOL Multiphysics Reference
Manual
• Isotropic Diffusion in the COMSOL Multiphysics Reference Manual
• Domain, Boundary, Point, and Pair Nodes for the Euler–Euler Model
Interfaces
• Theory for the Euler-Euler Model Interfaces

Domain, Boundary, Point, and Pair Nodes for the Euler–Euler Model
Interfaces
have the following domain, boundary, point, and pair nodes 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).

• Flow Continuity • Mass Transfer

• Gravity • Outlet
• Initial Values • Phase Properties
• Inlet • Volume Force
• Interior Wall • Wall

The following nodes are described for the Laminar Flow interface:

• Pressure Point Constraint

496 | CHAPTER 7: FLUID FLOW INTERFACES

• 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.

Phase Properties
The Phase Properties node has the material properties settings for the pure continuous
and dispersed phases. It also has settings for the viscosity models for each of the two
interpenetrating phases and the drag model. When the dispersed phase consists of solid
particles, it also has settings for the solid pressure model.

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 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 EULER-EULER MODEL INTERFACE | 497

 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

MATERIALS
Select the materials to use for the material properties of the continuous phase and the
dispersed phase respectively (when they are defined to take their values From material).
By default, the default material used for the Continuous phase is the Domain material.
This corresponds to the material currently applied to the domain in question. The
Dispersed phase uses None per default. A valid material must be selected instead.

Other materials present can be selected from the Continuous phase or Dispersed phase
list in order to use that material’s properties for the liquid or gas, respectively.

CONTINUOUS PHASE PROPERTIES

Density, Continuous Phase

The default Density, continuous phase c (SI unit: kg/m3) uses values From material.
For User defined enter another value or expression.

Dynamic Viscosity, Pure Continuous Phase

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. The dynamic viscosity of the pure
continuous phase refers to the viscosity the fluid would have in the absence of the
dispersed phase.

The default Dynamic viscosity, pure continuous phase c (SI unit: Pa·s) uses values From
material. The value of the viscosity is then the value defined for the material selected in
the Materials section for the continuous phase. For User defined define a different value
or expression.

498 | CHAPTER 7: FLUID FLOW INTERFACES

DISPERSED PHASE PROPERTIES
The default Density, dispersed phase d (SI unit: kg/m3) uses values From material. For
User defined enter another value or expression.

Enter a value or expression for the Diameter of particles/droplets dd (SI unit: m). The
default is 103 m (1 mm).

The Dynamic viscosity, pure dispersed phase d (SI unit: Pa·s) field is
available when Liquid droplets/bubbles is selected as the Dispersed phase in .

The default uses values From material. The value of the viscosity is then
the value defined for the material selected in the Materials section for the
dispersed phase. For User defined define a different value or expression.

VISCOSITY MODEL
Select a model for the Mixture viscosity — Krieger type (the default), Volume average
(available for liquid droplets and bubbles) or User defined. Krieger type is appropriate
for dispersed phases that do not form any pure phase regions. Volume average is more
appropriate when the dispersed phase effectively can become the only phase in some
regions.

• For Krieger type, select an option for Maximum packing concentration. The default is
to use  d,max = 1.0 for droplets and bubbles and  d,max = 0.62 for particles. Select
User defined to enter another value or expression for  d,max .
• For User defined enter a value or expression for the Mixture viscosity. The default
expression corresponds to the Krieger type viscosity with maximum packing equal
to 0.62.

Select a Dynamic viscosity model, continuous phase — Mixture viscosity (default), Pure
phase value or User defined. The Mixture viscosity option is appropriate when the
maximum packing is controlled by the mixture viscosity. The Pure phase value option
is more appropriate if the maximum packing is controlled in some other way, for
example by solid pressure. Select User defined to enter an expression for the Dynamic
viscosity model, continuous phase.

Select a Dynamic viscosity model, dispersed phase — Mixture viscosity (default), Pure
phase value (available for bubbles and droplets), Gidaspow (available for solid particles)
m
or User defined. The Gidaspow model prescribes  d = 0.5 d which basically
m
prescribes a small value for  d and should be combined with a solid pressure model.

THE EULER-EULER MODEL INTERFACE | 499

 DRAG MODEL
The models are described in . When the dispersed phase corresponds to Solid particles,
the Schiller-Naumann, Hadamard-Rybczynzki, Ishii-Zuber, Gidaspow, and Haider-Levenspiel
models are available. For Liquid droplets/bubbles, the Schiller-Naumann,
Hadamard-Rybczynzki, Ishii-Zuber, Tomiyama et al. models are available. Select the
User-defined drag coefficient option to specify an expression for the drag coefficient CD.

• The Schiller-Naumann is valid for dispersed, rigid spheres and can be used for particle
Reynolds numbers less than approximately 2.5·105. The Schiller-Naumann model
is a general purpose model for diluted flows.
• The Hadamard-Rybczynzki is appropriate for diluted flows at low Reynolds numbers.
• The Ishii-Zuber model can for solid particles be regarded as a generalization of the
Schiller-Naumann model in that it can be used also for dense flows. For droplets and
bubbles, the Ishii-Zuber model also takes deformation of the fluid particles into
account. The deformation depends on the Surface tension coefficient, . Use a
predefined expression, select Library coefficient, liquid/gas interface or Library
coefficient, liquid/liquid interface. Then select an option from the list that displays
below (for example, Water/Air, Glycerol/Air and so forth). For User defined enter a
value or expression for the surface tension coefficient  (SI unit: N/m).
• The Gidaspow model describes the drag force coefficient for dispersed phase flows
for all concentrations of the dispersed solid, including high concentrations.
• The Haider-Levenspiel model describes non-spherical particles for low and moderate
particle Reynolds numbers. Enter a value between 0 and 1 for the Sphericity Sp
(dimensionless).
• The Tomiyama et al. model describes the drag for diluted droplets and bubbles for
any particle Reynolds number. The correlation is available in three versions, Pure
fluid, Slightly contaminated fluid and Contaminated fluid. The Tomiyama et al. model
depends on the Surface tension coefficient,  that is selected in the same way as for
the Ishii-Zuber model.

SOLID PRESSURE MODEL

The solid pressure models the particle dispersion due to collisions and friction between
the solid particles. Details of the implemented models are described in .

500 | CHAPTER 7: FLUID FLOW INTERFACES

This section is available when Solid particles is selected as the Dispersed phase in . Select
a Solid pressure model ps.

• The No solid pressure (the default) disables solid pressure and leaves the collision to
be described by a mixture viscosity. This option is appropriate for solid suspension,
typically solids suspended in liquids.
• The other options, Gidaspow-Ettehadieh, Gidaspow, Ettehadieh and User defined
modulus of elasticity describes particle-particle interaction for dispersed solids,
typically solid particles in gas flows. These options should be combined with the
m
Gidaspow model or a small user defined value for  d .
• For User defined modulus of elasticity enter an expression for the Modulus of elasticity,
G (SI unit: N/m2).

MIXING LENGTH LIMIT

When the Mixing length limit lmix,lim is set to Automatic, the mixing length limit is
evaluated as the shortest side of the geometry bounding box. If the geometry is, for
example, a complicated system of slim entities, this measure can be too high. In such
cases, it is recommended that the mixing length limit is defined manually. Select Manual
to enter a different value or expression.

Initial Values
The Initial Values node adds initial values for the velocity fields for the continuous and
dispersed phases, the pressure, and the volume fraction of the dispersed phase that can
serve as initial conditions for a transient simulation or as an initial guess for a nonlinear
solver.

INITIAL VALUES
Enter initial values or expressions in the tables for each component of:

• Velocity field, continuous phase uc

• Velocity field, dispersed phase ud

Enter initial values or expressions for:

• Pressure p
• Volume fraction, dispersed phase phid

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 Mass Transfer
Use the Mass Transfer node to include mass transfer from the dispersed phase to the
continuous phase.

MASS TRANSFER
Select a Mass transfer model — User defined (the default) or Nonequilibrium model. For
User defined enter a value or expression for the Mass transfer from dispersed to
continuous phase mdc (SI unit: kg/(m3·s)). The default is 0 kg/(m3·s).

Nonequilibrium Model
For Nonequilibrium model enter values or expressions for each of the following:

• Equilibrium volume fraction in dispersed phase  eq. The default is 0.

• Inverse time scales fc and fd (SI unit: 1/s). The default is 0 s-1.
The mass transfer is modeled as

m dc =  d  max  f c   d –  eq  0  – max  f d   eq –  d  0  

Interphase Velocity
Select Dispersed phase velocity field (the default) or User defined. For User defined enter
a value or expression for each component of the interphase velocity u int .

Gravity
The Gravity node adds the gravity force vector to the right-hand side of the momentum
equations; cg for the continuous phase and dg for the dispersed phase.

Gravity nodes are mutually exclusive, that is, there can only be one active Gravity node
per domain.

GRAVITY
Enter the components of the Gravity vector, g (SI unit: m/s2). For 2D components
the default Gravity vector is defined as 0-g_const. Here g_const is a physical
constant equal to 9.8066 m/s2. For 3D and 2D axisymmetric components, the gravity
acts in the negative z direction by default.

Volume Force
The Volume Force node specifies the volume forces on the right-hand side of the
momentum equations; Fc for the continuous phase and Fd for the dispersed phase. It

502 | CHAPTER 7: FLUID FLOW INTERFACES

may for example be used to add user defined interaction forces (in addition to the
interphase drag force).

If several volume force nodes are added to the same domain, the sum of all
contributions are added to the respective momentum equations.

Wall
The Wall node includes a set of boundary conditions to describe the flow conditions
at a solid wall. The conditions for each phase are selected separately.

CONTINUOUS PHASE BOUNDARY CONDITION

Select a Continuous Phase Condition — No slip (the default), or Slip.

No Slip
A No slip condition models a wall where the velocity of the continuous phase relative
to the wall velocity is zero. For a stationary wall, it sets the velocity of the continuous
phase to zero:

uc = 0

For turbulent flows, wall functions are used to model the thin region near solid (no
slip) walls with high gradients in the flow variables

Slip
The Slip option prescribes a no-penetration condition. For a stationary wall,
u c  n = 0 . It is implicitly assumed that there are no viscous effects at the slip wall and
hence, no boundary layer develops.

Leakage
ꞏ
Select the Leakage check box to specify an Inward continuous phase mass flux, m c (SI
2 ꞏ
unit: kg(m ·s)). This option is intended for small values of m c . For large mass fluxes,
select us an Inlet feature instead.

DISPERSED PHASE BOUNDARY CONDITION

Select a Dispersed velocity boundary condition — No slip (the default), or Slip. The
conditions prescribed for the velocity of the dispersed phase correspond to those
described for the continuous phase above.

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 Dispersed Phase Boundary Condition
The Dispersed Phase Boundary Condition defines the condition at the wall for the
volume fraction of the dispersed phase.

• No dispersed phase flux prescribes a zero flux condition at the wall.

ꞏ
• Select Leakage to prescribe an Inward dispersed phase mass flux, m d (SI unit: kg
2 ꞏ
(m ·s)). This option is intended for small values of m d . For large mass fluxes, select
an Inlet feature instead.

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 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
associated wall to move. An additional Moving Mesh interface needs to be added 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; that is,
the surface is sliding in its 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.

504 | CHAPTER 7: FLUID FLOW INTERFACES

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

Inlet
The Inlet node prescribes the flow and turbulence conditions (when applicable) at a
boundary where one or both phases enter the adjacent domain.

TWO-PHASE INLET TYPE

Selecting Mixture as the Two-Phase Inlet Type, inlet conditions are prescribed for both
phases. Selecting Continuous phase or Dispersed phase, inlet conditions are prescribed
for the corresponding phase, while wall conditions are applied to the remaining phase.

CONTINUOUS PHASE
The options available in this section are based on the Two-phase inlet type selected.

When Mixture or Continuous phase is selected as the Two-phase inlet typ the Velocity
field, continuous phase uc0 is prescribed.

When Dispersed phase is selected as the Two-phase inlet type, the conditions applied to
the continuous phase are No slip (uc0) or Slip (uc·n0, and no viscous stresses in the
tangential directions).

DISPERSED PHASE
The options available in this section are based on the Two-phase inlet type selected.

When Mixture or Dispersed phase is selected as the Two-phase inlet type, the Velocity
field, dispersed phase ud0.

The Dispersed phase boundary condition can be Volume fraction, Mass flux or No flux.

• For Volume fraction, specify the Dispersed phase volume fraction,  d0, at the inlet.
This option locks the value of  d, but the exact flux depends on the dispersed phase
velocity, ud0.
ꞏ
• For Mass flux, prescribe describe the Inward dispersed phase mass flux, m d (SI unit:
2
kg(m ·s)). This option prescribes the flux for the dispersed phase, but the resulting
volume fraction at the inlet depends on the dispersed phase velocity, ud0.
When Continuous phase is selected as the Two-phase inlet type, the conditions applied
to the dispersed phase are No slip (ud0) or Slip (ud·n0, and no viscous stresses in the
tangential directions).

THE EULER-EULER MODEL INTERFACE | 505

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

Outlet
This node is used to prescribe conditions at boundaries where the two-phase mixture
exits the computational domain. The settings available in the node specifies conditions
for the entire mixture, as opposed to the Inlet, Outlet and Wall nodes where the
conditions for can be specified for each phase individually.

MIXTURE BOUNDARY CONDITION

Select Mixture boundary conditions — Pressure, no viscous stress, Pressure, normal flow,
Velocity, Degassing, or Filtration.

Pressure Conditions
When Pressure, no viscous stress or Pressure, normal flow is selected as the Mixture
boundary condition, specify the Pressure p0 (SI unit: Pa) at the outlet. Note that the
prescribed pressure should be consistent with the reference pressure level specified at
the interface level as well as consistent with present volume forces (including gravity).

Velocity
Select Velocity to specify the Velocity field, continuous phase uc0 (SI unit: m/s) together
with the Velocity field, dispersed phase ud (SI unit: m/s) at the outlet.

Degassing and Filtration

Selecting Degassing allows the dispersed phase to exit the domain but prevents the
continuous phase from exiting. This is achieved through a pressure (p0), no viscous
stress condition for the dispersed phase, in combination with a no penetration
condition for the continuous phase.

Selecting Filtration on the other hand allows the continuous phase to exit the domain
but prevents the dispersed phase from exiting. This is achieved through a pressure (p0),

506 | CHAPTER 7: FLUID FLOW INTERFACES

no viscous stress condition for the continuous phase, in combination with a no
penetration condition for the dispersed phase.

Pressure, no viscous stress is the least constraining option and allows the
flow to exit the domain in non-normal directions.

Pressure, normal flow restricts the flow to be completely normal to the

outlet boundary. This option can influence the flow quite a bit upstream
of the inlet.

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

Interior Wall
The Interior Wall boundary condition can only be applied on interior boundaries.

It is similar to the Wall boundary condition available on exterior boundaries except

that it applies on both sides of an interior boundary. It allows discontinuities of the
dependent variables across the boundary. The Interior Wall boundary condition can be
used to avoid meshing thin structures by applying no-slip conditions on interior curves
and surfaces instead. Slip conditions and conditions for a moving wall can also be
prescribed. It is compatible with laminar and turbulent flow. The conditions for each
phase are selected separately.

CONTINUOUS PHASE BOUNDARY CONDITION

Select a Continuous Phase Condition — No slip (the default), or Slip.

No Slip
A No slip condition models a wall where the velocity of the continuous phase relative
to the wall velocity is zero. For an interior stationary wall, it sets the velocity of the
continuous phase to zero on both sides of the wall:

uc = 0

For turbulent flows, wall functions are used to model the thin region near solid walls
with high gradients in the flow variables.

THE EULER-EULER MODEL INTERFACE | 507

 Slip
Slip prescribes a no-penetration condition. For a stationary interior wall, u c  n = 0
on both sides.

DISPERSED PHASE BOUNDARY CONDITION

Select a Dispersed velocity boundary condition — No slip (the default), or Slip. The
conditions prescribed for the velocity of the dispersed phase correspond to those
described for the continuous phase above.

Dispersed Phase Boundary Condition

The Dispersed phase boundary condition is set to No dispersed phase flux.

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

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

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.

A Wall Fallback feature subnode is added by default and it applies to the parts of the
pair boundaries where a source boundary lacks a corresponding destination boundary

508 | CHAPTER 7: FLUID FLOW INTERFACES

and vice versa. The Wall feature can be overridden by any other boundary condition
that applies to exterior boundaries. By right-clicking the Flow Continuity node,
additional Fallback feature subnodes can be added.

THE EULER-EULER MODEL INTERFACE | 509

 Theory for the Laminar Flow and
Creeping Flow Interfaces
The theory for the Single-Phase Flow, Laminar Flow, and Viscoelastic Flow interfaces
is described in this section:

• General Single-Phase Flow Theory

• Compressible Flow
• Weakly Compressible Flow
• The Mach Number Limit
• Incompressible Flow
• The Reynolds Number
• Theory for the Wall Boundary Condition
• Prescribing Inlet and Outlet Conditions
• Mass Flow
• 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.

510 | CHAPTER 7: 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

-
----- +    u  = 0 (7-13)
t

u
 ------- +   u   u =    – pI + K  + F (7-14)
t

T T  p
C p  ------- +  u   T = –    q  + K:S – ---- -------  ------ +  u   p + Q (7-15)
 t   T p  t 

where

•  is the density (SI unit: kg/m3)

• u is the velocity vector (SI unit: m/s)
• p is pressure (SI unit: Pa)
• 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 (7-16)

n m

This is sometimes referred to as the double dot product.

Equation 7-13 is the continuity equation and represents conservation of mass.

Equation 7-14 is a vector equation which represents conservation of momentum.
Equation 7-15 describes the conservation of energy, formulated in terms of

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 511
 temperature. This is an intuitive formulation that facilitates boundary condition
specifications.

To close the equation system, Equation 7-13 through Equation 7-15, 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 = 2S – ---     u I (7-17)
3

The dynamic viscosity,  (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 7-15 is decoupled
from Equation 7-13 and Equation 7-14.

2D AXISYMMETRIC FORMULATIONS
A 2D axisymmetric formulation of Equation 7-13 and Equation 7-14 requires   
to be zero. That is, there must be no gradients in the azimuthal direction. A common
additional assumption is, however, that u  = 0 . In such cases, the  -equation can be
removed from Equation 7-14. The resulting system of equations is both easier to
converge and computationally less expensive compared to retaining the  -equation.
The default 2D axisymmetric formulation of Equation 7-13 and Equation 7-14
therefore assumes that

512 | CHAPTER 7: FLUID FLOW INTERFACES

    = 0
u = 0

Compressible Flow
The equations of motion for a single-phase fluid are the continuity equation:

-
----- +    u  = 0 (7-18)
t

and the momentum equation:

u
 ------- + u  u = – p +      u +  u  T  – ---     u I + F
2
(7-19)
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

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

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 513
 instantaneously propagated throughout the entire domain. This results in a parabolic
equation system.

The momentum equation, Equation 7-19, is parabolic for unsteady flow and elliptic
for steady flow, whereas the continuity equation, Equation 7-18, 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 7-19 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.

The practical Mach number limit is lower than one, however. 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,  is constant or nearly constant. This is the case for
all liquids under normal conditions and also for gases at low velocities. For constant ,
Equation 7-18 reduces to

  u = 0 (7-20)

and Equation 7-19 becomes

514 | CHAPTER 7: FLUID FLOW INTERFACES

 u T
 +   u   u =    – pI +   u +  u    + F (7-21)
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:

UL
Re = ------------


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  uh2 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: spf.cellRe).

Theory for the Wall Boundary Condition

See Wall for the node settings.

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 515
 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 +   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 =   u +  u  T n

expressing that there is no flow across the boundary and no viscous stress in the
tangential direction.

For a moving wall with translational velocity utr, u in the above equations is replaced
by the relative velocity urel  uutr.

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:

516 | CHAPTER 7: FLUID FLOW INTERFACES

 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


K nt = – --- u slip


where K nt = K n –  K n  n wall n wall , K n = Kn wall and K is the viscous stress tensor.

is a slip length, and u slip = u –  u  n wall n wall is the velocity tangential to the wall.
The boundary condition does not set the tangential velocity component to zero;
however, the extrapolated tangential velocity component is 0 at a distance  outside
the wall.

The Slip Length setting is per default set to Factor of minimum element length. The slip
length  is then defined as  = 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  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

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 517
 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
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.

518 | CHAPTER 7: FLUID FLOW INTERFACES

• 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
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 + 2 --------- = F n (7-22)
n

where unn is the normal derivative of the normal velocity component.

Equation 7-22 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 7-22 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 7-22, all but one
velocity component must be specified. For low Reynolds numbers, this can be specified
by a vanishing tangential stress condition:

u t
 -------- = 0
n

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 519
 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
 -------- = 0
n

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

Mass Flow
The Mass flow boundary condition constrains the mass flowing into the domain across
an inlet boundary. The mass flow can be specified in a number of ways.

520 | CHAPTER 7: FLUID FLOW INTERFACES

POINTWISE MASS FLUX
The pointwise mass flux sets the velocity at the boundary to:

mf
u = – ------- n


where mf is the normal mass flux and is the density.

MASS FLOW RATE

The mass flow rate boundary condition sets the total mass flow through the boundary
according to:

–  dbc   u  n  dS = m


where dbc (only present in the 2D Cartesian axis system) is the boundary thickness
normal to the fluid-flow domain and m is the total mass flow rate.

In addition to the constraint on the total flow across the boundary, the tangential
velocity components are set to zero on the boundary

un = 0 (7-23)

STANDARD FLOW RATE

The standard flow rate boundary condition specifies the mass flow as a standard
volumetric flow rate. The mass flow through the boundary is set by the equation:


–  dbc -------
 st
 u  n  dS = Q sv


where dbc (only present in the 2D component Cartesian axis system) is the boundary
thickness normal to the fluid-flow domain, st is the standard density, and Qsv is the
standard flow rate. The standard density is defined by one of the following equations:

Mn
 st = --------
Vn

p st M n
 st = -----------------
RT st

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 521
 where Mn is the mean molar mass of the fluid, Vn is the standard molar volume, pst is
the standard pressure, R is the universal molar gas constant, and Tst is the standard
temperature.

Equation 7-23 or Equation 7-24 is also enforced for compressible and incompressible
flow, respectively, ensuring that the normal component of the viscous stress and the
tangential component of the velocity are zero at the boundary.

Fully Developed Flow (Inlet)

The Fully developed flow boundary condition can be understood from the following
figure:

pinl 

The flow to the domain  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

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:

 –   tu +  tu  T  + p  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, . This is
most notably if the flow is strongly curved just downstream of the inlet. This can for

522 | CHAPTER 7: FLUID FLOW INTERFACES

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

ˆ
  u  n + U av P 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  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 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
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:

 pexit

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 523
 The flow to the domain  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:

 –   tu +  tu  T  + p  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, . 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

ˆ
  u  n + U av P 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:

524 | CHAPTER 7: FLUID FLOW INTERFACES

    u +  u  T  – 2
---     u I n = 0
 3 

   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 +    u +  u  T  – 2
---     u I  n = – f 0 n
  3 

 – pI +   u +  u  T  n = – f 0 n

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 = 2 ---------- + f 0 (7-24)
n

If unn is small, Equation 7-24 states that p  f0.

The Normal Stress condition is the mathematically correct version of the Pressure
Conditions condition (Ref. 4), but it is numerically less stable.

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 525
 Pressure Boundary Condition
For single-phase flow, a mathematically correct natural boundary condition for outlets
is

 – pI +   u +  u  T  – 2
---     u I n = – p 0 n (7-25)
 3 

 – pI +   u +  u  T  n = – p 0 n (7-26)

using the compressible/weakly compressible and the incompressible formulation,

respectively.

This is a normal stress condition together with a no-tangential-stress condition. When

  ,Equation 7-25 or Equation 7-26 can be supplemented with a tangential velocity
condition

ut  (7-27)

If so, the no-tangential-stress condition is overridden. An issue with Equation 7-25 or

Equation 7-26 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

---     u I n = – pˆ 0 n
 – pI +   u +  u  T  – 2
 3 
, (7-28)
 – pI +   u +  u  T  n = – pˆ 0 n
pˆ  p
0 0

the normal stress is adjusted to keep

un0 (7-29)

Equation 7-28 effectively means that the prescribed pressure is p0 if un , but
smaller at locations where un . This means that Equation 7-28 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.

526 | CHAPTER 7: FLUID FLOW INTERFACES

A pressure condition can also be applied at an inlet. In this case, either the normal stress
is prescribed

n  – pI +   u +  u  T  – ---     u I n = – pˆ 0
T 2
 3 
(7-30)
n  – pI +   u +  u  T  n = – pˆ 0
T

pˆ  p
0 0

together with the tangential condition in Equation 7-27, or, a general flow direction
is prescribed.

---     u I n = – pˆ 0  r  n 
T  – pI +   u +  u  T  – 2
ru
 3  u
ˆ r  n
T  – pI +   u +  u  T  n = – p
ru 0 u
(7-31)
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
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 – ---  u (7-32)
2

The equation is imposed with two options: Average and Pointwise.

In the first option, pstat is prescribed by:

T T
n  – pI +   u +  u  T  n = n  – p stat I +   u +  u  T  n (7-33)

where ptot and u2 are averaged over the boundaries using the aveop operator:

1 2
p stat = aveop  p tot  – ---   aveop  u 
2

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 527
 For the second option, Equation 7-32 is prescribed pointwise.

See Inlet, Outlet, Open Boundary, and No Viscous Stress 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
ꞏ
A point source is theoretically formed by taking a mass injection/ejection, Q (SI unit:
3
kg/(m ·s)), in a small volume V and then letting the size of the volume tend to zero
while keeping the total mass flux constant. Given a point source strength, qꞏ p (SI unit:
kg/s), this can be expressed as

ꞏ ꞏ
lim
V  0  Q = qp (7-34)
V

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

qꞏ p test  p 
ꞏ
is added to a point in the geometry. As can be seen from Equation 7-34, Q must tend
to plus or minus infinity as V tends to zero. This means that in theory the pressure
also tends to plus or minus infinity.

528 | CHAPTER 7: FLUID FLOW 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 7-34 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
ꞏ
A line source can theoretically be formed by assuming a source of strength Q (SI unit:
3
kg/(m ·s)), located within a tube with cross-sectional area S and then letting S tend
to zero, while keeping the total mass flux per unit length constant. Given a line source
strength, qꞏ l (SI unit: kg/(m·s)), this can be expressed as

ꞏ
lim Q = qꞏ l (7-35)
S  0
S

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 on the fluid resulting from the physical object volume are
neglected.

The weak contribution

qꞏ 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.

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 529
 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 7-19 or Equation 7-21) 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
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, t

530 | CHAPTER 7: FLUID FLOW INTERFACES

(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 t2 in the
time-scale tensor with measures of type  1   t̃  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
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.

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 531
 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.

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.

532 | CHAPTER 7: FLUID FLOW INTERFACES

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.

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

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 533
 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-
method instead. Generalized- 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- are per default set to automatically adjust the time step.
While this works well for many models, extra efficiency and accuracy can often be
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 7-21
reduces to:

T
  u   u =    – pI +   u +  u    + F (7-36)

534 | CHAPTER 7: FLUID FLOW INTERFACES

Solving Equation 7-36 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 7-36:

u – nojac  u  T
 --------------------------------- +   u   u =    – pI +   u +  u    + F
t̃

where t̃ 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 t̃ of a time-dependent
solver.

Pseudo time stepping is not active per default. The pseudo time step t̃ can be chosen
individually for each element based on the local CFL number:

h
t̃ = 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.

The default manual expression is

1.3 min  niterCMP 9  +

if  niterCMP  20 9  1.3 min  niterCMP – 20 9  0  + (7-37)
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

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 535
 then takes it to 1060. Equation 7-37 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.

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
= F  t x 
d x dx
m
dt2  dt 

536 | CHAPTER 7: FLUID FLOW INTERFACES

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 2r
Re p = ------------------------------


where u is the velocity of the fluid, up the particle velocity, r the particle radius,  the
fluid density, and  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 = r  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.

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.

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 537
 6. Y. Bazilevs, V.M. Calo, T.E. Tezduyar, and T.J.R. Hughes, “YZ Discontinuity
Capturing for Advection-dominated Processes with Application to Arterial Drug
Delivery”, Int.J.Num. 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.

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.

538 | CHAPTER 7: FLUID FLOW INTERFACES

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 539
 Theory for the Darcy’s Law Interface
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

540 | CHAPTER 7: FLUID FLOW INTERFACES

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:


u = – --- p (7-38)


In this equation, u is the Darcy’s velocity or specific discharge vector (SI unit: m/s);
 is the permeability of the porous medium (SI unit: m2);  is the fluid’s dynamic
viscosity (SI unit: Pa·s); p is the pore pressure (SI unit: Pa) and  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 https://www.comsol.com/products/specifications/.

The Darcy’s Law interface combines Darcy’s law with the continuity equation

 
 p  +    u  = Q m (7-39)
t

In the above equation,  is the fluid density (SI unit: kg/m3), p 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:

THEORY FOR THE DARCY’S LAW INTERFACE | 541

 
u = – ---  p + g  (7-40)


• 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
https://www.comsol.com/products/specifications/.
• 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 7-38) into the continuity equation produces the
generalized governing equation

    +    – ---  p  = Q (7-41)
t p  m

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 7-41

    =  -----
-  p
p t +  t
--------
t p

Define the porosity and the density as functions of the pressure, and apply the chain
rule

  p  p  p p
 p ------ +  -------- =  p ------ ------ +  -------- ------
t t p t p t

Insert the definition of fluid compressibility fp to the right-hand side and
rearrange to arrive at

  p   p p p
---------------- =    p  f + -------- ------ = S ------
t p t t

542 | CHAPTER 7: FLUID FLOW INTERFACES

Using this relation, the generalized governing equation (Equation 7-41) takes the
following form:

p 
S ------ +    – ---  p  = Q m (7-42)
t 

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 7-42 using the Storage Model node, which explicitly
includes an option to define S as the linearized storage (SI unit: 1/Pa) using the
compressibility of fluids and porous matrix.

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://
www.comsol.com/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, u, (also termed the seepage velocity) defined as u  up, where p is the
porosity.

References for the Darcy’s Law Interface

1. J. Bear, Hydraulics of Groundwater, McGraw-Hill, 1979.

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.

THEORY FOR THE DARCY’S LAW INTERFACE | 543

 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.

544 | CHAPTER 7: FLUID FLOW INTERFACES

Theory for 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.

THEORY FOR THE FREE AND POROUS MEDIA FLOW INTERFACE | 545
 Theory for 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:

546 | CHAPTER 7: FLUID FLOW INTERFACES

      +    u  = Q (7-43)
t p m

-  u
+  u    ----- =
u
----
p   t  p
(7-44)
1 T 2   Q m
–  p +   -----    u +  u   – ---     u I  –   – 1  + -------- u +F
p  3    p2 

In these equations:

•  (SI unit: kg/(m·s)) is the dynamic viscosity of the fluid

• u (SI unit: m/s) is the velocity vector
•  (SI unit: kg/m3) is the density of the fluid
• p (SI unit: Pa) is the pressure
• p is the porosity
•  (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
p) on the left-hand side of Equation 7-44 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  uu, on the right-hand side of Equation 7-44.

In case of a flow with variable density, Equation 7-43 and Equation 7-44 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


    + u   = 0
t p

and the continuity equation (Equation 7-43) reduces to

THEORY FOR THE BRINKMAN EQUATIONS INTERFACE | 547

   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.

548 | CHAPTER 7: FLUID FLOW INTERFACES

T he o r y f o r th e Bu b b l y Fl ow In t erface
The Bubbly Flow interfaces are suitable for macroscopic modeling of mixtures of
liquids and gas bubbles. These physics interfaces solve for the averaged volume fraction
occupied by each of the two phases, rather than tracking each bubble in detail. Each
phase has its own velocity field.

In this section:

• The Bubbly Flow Equations

• Turbulence Modeling in Bubbly Flow Applications
• References for the Bubbly Flow Interfaces

The Bubbly Flow Equations

The two-fluid Euler-Euler Model is a general, macroscopic model for two-phase fluid
flow. It treats the two phases as interpenetrating media, tracking the averaged
concentration of the phases. One velocity field is associated with each phase. A
momentum balance equation and a continuity equation describe the dynamics of each
of the phases. The bubbly flow model is a simplification of the two-fluid model, relying
on the following assumptions:

• The gas density is negligible compared to the liquid density.

• The motion of the gas bubbles relative to the liquid is determined by a balance
between viscous drag and pressure forces.
• The two phases share the same pressure field.

Based on these assumptions, the momentum and continuity equations for the two
phases can be combined and a gas phase transport equation is kept in order to track
the volume fraction of the bubbles. The momentum equation is

u l
l l +  l  l u l  u l =
t
(7-45)
= – p +    l   l +  T   u l + u l – ---    u l I +  l  l g + F
T 2
3

In Equation 7-45, the variables are as follows:

• ul is the velocity vector (SI unit: m/s)

THEORY FOR THE BUBBLY FLOW INTERFACE | 549

 • p is the pressure (SI unit: Pa)
•  is thephase volume fraction (SI unit: m3/m3)
•  is the density (SI unit: kg/m3)
• g is the gravity vector (SI unit: m/s2)
• F is any additional volume force (SI unit: N/m3)
• l is the dynamic viscosity of the liquid (SI unit: Pa·s), and
• T is the turbulent viscosity (SI unit: Pa·s)

The subscripts “l” and “g” denote quantities related to the liquid phase and the gas
phase, respectively.

The continuity equation is

 
  + g g  +    l l ul + g g ug  = 0 (7-46)
t l l

and the gas phase transport equation is

 g  g
--------------- +     g  u g  = – m gl (7-47)
t g

where mgl is the mass transfer rate from the gas to the liquid (SI unit: kg/(m3·s)).

For low gas volume fractions (  g  0.01 ), you can replace the momentum equations,
Equation 7-45, and the continuity equation, Equation 7-46, by

u l
l +  l u l  u l =
t (7-48)
T
= – p +      l +  T   u l + u l   +  l  l g + F

l   ul = 0 (7-49)

By default, the Laminar Bubbly Flow interface uses Equation 7-48 and 7-49. To
switch to Equation 7-45 and 7-46, click to clear the Low gas concentration check box
under the Physical Model section.

The physics interface solves for ul, p, and

̃ g =  g  g

the effective gas density. The gas velocity ug is the sum of the following velocities:

550 | CHAPTER 7: FLUID FLOW INTERFACES

 u g = u l + u slip + u drift (7-50)

where uslip is the relative velocity between the phases and udrift is a drift velocity (see
Turbulence Modeling in Bubbly Flow Applications). The physics interface calculates
the gas density from the ideal gas law:

 p + p ref M
 g = ------------------------------
RT

where M is the molecular weight of the gas (SI unit: kg/mol), R is the ideal gas
constant (8.314472 J/(mol·K)), pref a reference pressure (SI unit: Pa), and T is
temperature (SI unit: K). pref is a scalar variable, which by default is 1 atm (1
atmosphere or 101,325 Pa). The liquid volume fraction is calculated from

l = 1 – g

When there is a drift velocity, it has the form

 g
u drift = – D gc ---------- (7-51)
g

where

T
D gc = ------------
l T

Here, T is the turbulent viscosity, and T is the turbulent Schmidt number.

Inserting Equation 7-51 and Equation 7-50 into Equation 7-47 gives

 g  g
--------------- +     g   u l + u slip   =    D gc  g  g  – m gl
t g

That is, the drift velocity introduces a diffusive term in the gas transport equation. This
is how the equation for the transport of the volume fraction of gas is actually
implemented in the physics interface.

The bubbly-flow equation formulation is relatively simple, but it can display some
nonphysical behavior. One is artificial accumulation of bubbles, for example, beneath
walls where the pressure gradient forces the bubbles upward, but the bubbles have no
place to go and there is no term in the model to prevent the volume fraction of gas
from growing. To prevent this from happening, ̃ is set to l in the laminar case. The

THEORY FOR THE BUBBLY FLOW INTERFACE | 551

 only apparent effect of this in most cases where the bubbly-flow equations are
applicable is that nonphysical accumulation of bubbles is reduced. The small effective
viscosity in the transport equation for  g has beneficial effects on the numerical
properties of the equation system.

MASS TRANSFER AND INTERFACIAL AREA

It is possible to account for mass transfer between the two phases by specifying an
expression for the mass transfer rate from the gas to the liquid mgl (SI unit: kg/
(m3·s)).

The mass transfer rate typically depends on the interfacial area between the two phases.
An example is when gas dissolves into a liquid. In order to determine the interfacial
area, it is necessary to solve for the bubble number density (that is, the number of
bubbles per volume) in addition to the phase volume fraction. The Bubbly Flow
interface assumes that the gas bubbles can expand or shrink but not completely vanish,
merge, or split. The conservation of the number density n (SI unit: 1/m3) then gives

n
+    n  u l + u slip   =    D gc n 
t

The number density and the volume fraction of gas give the interfacial area per unit
volume (SI unit: m2/m3):

13 23
a =  4n   3 g 

SLIP MODEL
The simplest possible approximation for the slip velocity uslip is to assume that the
bubbles always follow the liquid phase; that is, uslip  0. This is known as
homogeneous flow.

A better model can be obtained from the momentum equation for the gas phase.
Comparing size of different terms, it can be argued that the equation can be reduced
to a balance between the viscous drag force, fD and the pressure gradient (Ref. 3), a so
called pressure-drag balance:

 l p = f D (7-52)

Here fD can be written as

552 | CHAPTER 7: FLUID FLOW INTERFACES

 3 l
f D = – C d --- ------ u slip u slip (7-53)
4 db

where in turn db (SI unit: m) is the bubble diameter, and Cd (dimensionless) is the
viscous drag coefficient. Given Cd and db, Equation 7-52 can be used to calculate the
slip velocity. In practice, Equation 7-52 is multiplied by  l to reduce the slip velocity
for large values of  g .

Schwarz and Turner (Ref. 4) proposed a linearized version of Equation 7-53

appropriate for air bubbles of 1–10 mm mean diameter in water:

kg-
f D = – C W u slip C W = 5  10 4 --------- (7-54)
m3 s

The Hadamard-Rybczynski model is appropriate for small spherical bubbles with

diameter less than 2 mm, and bubble Reynolds number less than one. The model uses
the following expression for the drag coefficient (Ref. 5):

16 d b  l u slip
C d = ---------- , Re b = ---------------------------
Re b l

For bubbles with diameter larger than 2 mm, the model suggested by Sokolichin,
Eigenberger, and Lapin (Ref. 1) is a more appropriate choice:

0.622
C d = -----------------------------
1
------- + 0.235
Eö

where Eö is the Eötvös number

2
g l d b
Eö = ---------------


Here, g is the magnitude of the gravity vector and  the surface tension coefficient.

Turbulence Modeling in Bubbly Flow Applications

For most bubbly flow applications the flow field is turbulent. In that case, use a
turbulence model and solve for the averaged velocity field. The Bubbly Flow,
Turbulent Flow interfaces include the turbulence models described in Theory for the
Turbulent Flow Interfaces, but the material properties of the liquid phase are used. In
addition to the options of the single-phase flow model, in , , , , and it is also possible

THEORY FOR THE BUBBLY FLOW INTERFACE | 553

 to account for bubble-induced turbulence — that is, extra production of turbulence
due to relative motion between the gas bubbles and the liquid. The transport equation
for the turbulent kinetic energy, k, includes a source term Sk which accounts for
bubble-induced turbulence and is given by

S k = – C k  g p  u slip

The transport equation for the turbulent energy’s dissipation rate,  includes the
following source term:


C  S k ---
k

The following source term is added to the transport equation for the specific
dissipation rate, :


  S k ----
k

Suitable values for the model parameters Ck, C, and  are not as well established as
the parameters for single-phase flow. In the literature, values within the ranges
0.01 < Ck < 1, 1  C  1.92 have been suggested (Ref. 1), and  can be defined as
 = C – 1 .

The turbulent viscosity appears in the momentum equation and when adding a drift
term to the gas velocity:

 g
u drift = – D gc ----------
g

Using a turbulence model that solves for the turbulent kinetic energy, k, together with
a gas concentration that is not assumed to be low, the stress tensor contains an extra
contribution, and the momentum equations becomes

u l
l l +  l  l u l  u l =
t
(7-55)
 T 2  2
= – p +    l   l +  T  u l + u l – ---    u l I – ---  l  l kI +  l  l g + F
 3  3

554 | CHAPTER 7: FLUID FLOW INTERFACES

References for the Bubbly Flow Interfaces
1. A. Sokolichin, G. Eigenberger, and A. Lapin, “Simulations of Buoyancy Driven
Bubbly Flow: Established Simplifications and Open Questions”, AIChE Journal,
vol. 50, no. 1, pp. 24–49, 2004.

2. D. Kuzmin and S. Turek, Efficient Numerical Techniques for Flow Simulation in

Bubble Column Reactors, Institute of Applied Mathematics, University of Dortmund,
2000.

3. D. Kuzmin, S. Turek, and H. Haario, Finite Element Simulation of Turbulent

Bubbly Flows in Gas-liquid Reactors, Ergebnisberichte Angew, Math, 298, University
of Dortmund, 2005.

4. M.P. Schwarz and W.J. Turner, “Applicability of the Standard k- Turbulence Model
to Gas-stirred Baths”, Applied Mathematical Modelling, vol. 12, pp. 273–279, 1988.

5. C. Crowe, M. Sommerfeld, and Y. Tsuji, Multiphase Flows with Droplets and

Particles, CRC Press, 1998.

THEORY FOR THE BUBBLY FLOW INTERFACE | 555

 T he o r y f o r t h e Mi xt u re Mod el
Interface
The mixture model is a macroscopic two-phase flow model, in many ways similar to
the bubbly flow model. It tracks the averaged phase concentration, or volume fraction,
and solves a single momentum equation for the mixture velocity. It is suitable for
mixtures consisting of solid particles or liquid droplets immersed in a liquid.

The Mixture Model interface theory is described in this section:

• The Mixture Model Equations

• Dispersed Phase Boundary Condition Equations
• Turbulence Modeling in Mixture Models
• Slip Velocity Models
• References for the Mixture Model Interfaces

The Mixture Model Equations

In the Mixture Model interfaces the particle-fluid combination is regarded as a single
flowing continuum with macroscopic properties such as density and viscosity. The two
phases consist of one dispersed phase and one continuous phase. The mixture model
is valid if the continuous phase is a liquid, and the dispersed phase consists of solid
particles, liquid droplets, or gas bubbles. For gas bubbles in a liquid, however, the
bubbly flow model is preferable. The mixture model relies on the following
assumptions:

• The density of each phase is approximately constant.

• Both phases share the same pressure field.
• The particle relaxation time is short compared to the time-scales of the macroscopic
flow.

The mixture density is given by

 = c c + d d

556 | CHAPTER 7: FLUID FLOW INTERFACES

where

•  c and  d denote the volume fractions of the continuous phase and the dispersed
phase (SI unit: m3/m3), respectively
• c is the continuous phase density (SI unit: kg/m3), and
• d is the dispersed phase density (SI unit: kg/m3).

The volume flux for each phase is

jd = d ud

jc = c uc

where uc and ud (SI unit: m/s) are the continuous and the dispersed phase velocity
vectors, respectively.

In previous versions of COMSOL Multiphysics (prior to version 5.4, see

Mass-Averaged Mixture Velocity), the mixture velocity used was the mass-averaged
mixture velocity u (SI unit: m/s), defined as

c c uc + d d ud
u = -------------------------------------------- (7-56)


The mixture velocity used here is the volume-averaged flux density, or

volume-averaged mixture velocity j (SI unit: m/s), defined as

j = jd + jc

The continuity equation for the mixture is

 t +    u  = 0 (7-57)

In the Mixture Model interfaces it is assumed that the densities of both phases, c and
d, are constant, and therefore the following alternative form of the continuity
equation for the mixture is used

  j = m dc  ----- – ------
1 1
(7-58)
  c  d

The momentum equation for the mixture is

THEORY FOR THE MIXTURE MODEL INTERFACE | 557

 j t +   j   j +  c   j slip   j = –  p +    Gm + g + F
T
–     c  1 +  c  u slip j slip 

–  c   j   j slip +     D md  d  j + j slip m dc  ----- – ------

1 1
c d

where:

• j is the velocity vector (SI unit: m/s)

•  is the density (SI unit: kg/m3)
• p is the pressure (SI unit: Pa)
•  is the reduced density difference (SI unit: kg/kg)
• uslip is the slip velocity vector between the two phases (SI unit: m/s)
• jslip is the slip flux (SI unit: m/s)
• Gm is the sum of the viscous and turbulent stresses (SI unit: kg/(m·s2))
• Dmd is a turbulent dispersion coefficient (SI unit: m2/s)
• mdc is the mass transfer rate from the dispersed to the continuous phase (SI unit:
kg/(m3·s))
• g is the gravity vector (SI unit: m/s2), and
• F is any additional volume force (SI unit: N/m3)

The slip flux is defined for convenience as,

j slip =  d  c u slip (7-59)

Here, uslip (SI unit: m/s) denotes the relative velocity between the two phases. For
different available models for the slip velocity, see Slip Velocity Models.

The reduced density difference  is given by

d – c
 = -----------------
c

The sum of the viscous and turbulent stresses is

T 2 2
 Gm =   +  T   j + j  – ---   +  T     j I – --- kI (7-60)
3 3

558 | CHAPTER 7: FLUID FLOW INTERFACES

where (SI unit: Pa·s) is the mixture viscosity, T (SI unit: Pa·s) the turbulent viscosity,
and k (SI unit: m2/s2) is the turbulent kinetic energy, when available. If no turbulence
model is used, T and k equal zero

The transport equation for  d , the dispersed phase volume fraction, is

 
   +     d  d u d  =     d D md  d  – m dc (7-61)
t d d

where mdc (SI unit: kg/(m3·s)) is the mass transfer rate from the dispersed to the
continuous phase and Dmd is a turbulent dispersion coefficient (SI unit: m2/s) (see
Turbulence Modeling in Mixture Models), accounting for extra diffusion due to
turbulent eddies. When a turbulence model is not used, Dmd is zero. Assuming
constant density for the dispersed phase and using Equation 7-58, Equation 7-61 can
be rewritten as

  m dc 
 d  + j   d +    j slip  =    D md  d  – -------------- (7-62)
t d c

The continuous phase volume fraction  c is

c = 1 – d

MASS TRANSFER AND INTERFACIAL AREA

It is possible to account for mass transfer between the two phases by specifying an
expression for the mass transfer rate from the dispersed phase to the continuous mdc
(SI unit: kg/(m3·s)).

The mass transfer rate typically depends on the interfacial area between the two phases.
An example is when gas dissolves into a liquid. In order to determine the interfacial
area, it is necessary to solve for the dispersed phase number density (that is, the number
of particles per volume) in addition to the phase volume fraction. The Mixture Model
interface assumes that the particles can increase or decrease in size but not completely
vanish, merge, or split. The conservation of the number density n (SI unit: 1/m3) then
gives

n
+ j  n +    n c u slip  =    D md n  – nm dc  ----- – ------
1 1
t   c  d

The number density and the volume fraction dispersed particles give the interfacial area
per unit volume (SI unit: m2/m3):

THEORY FOR THE MIXTURE MODEL INTERFACE | 559

 13 23
a =  4n   3 d 

MASS-AVERAGED MIXTURE VELOCITY

In previous versions of COMSOL Multiphysics (prior to version 5.4), the mixture
velocity used was the mass-averaged mixture velocity u (SI unit: m/s), see
Equation 7-56. The continuity equation was

m dc
  c –  d      d  1 – c d u slip – D md  d  + ---------- +  c    u  = 0 (7-63)
d

and the transport equation for  d was

  m dc
 d  +     d u d  =    D md  d  – ---------- (7-64)
t d

The dispersed phase velocity vector ud and the mass fraction of the dispersed phase cd
are given by

u d = u +  1 – c d u slip

d d
c d = ------------


The continuity equation Equation 7-63 is incompatible with the no-penetration

condition of u at the walls, and u is not divergence-free. The volume-averaged velocity
j is solenoidal and Equation 7-58 is compatible with the no-penetration condition at
the walls (as long as there is no mass transfer or the densities of the two phases are
equal).

Dispersed Phase Boundary Condition Equations

In addition to the boundary conditions for the mixture, specify boundary conditions
for the dispersed phase on Wall, Inlet, and Outlet nodes. For these boundary types, the
boundary condition’s Settings window contains a Dispersed Phase Boundary
Condition section.

DISPERSED PHASE CONCENTRATION

This is the default for the Inlet node. Specify the dispersed phase volume fraction:

 d =  d0

560 | CHAPTER 7: FLUID FLOW INTERFACES

Enter the Dispersed phase volume fraction (dimensionless) in the  d0 field.

If Solve for interfacial area is selected under the Physical Model section, the dispersed
phase number density is also specified. The dispersed phase number density can be
specified directly,

n = n0

or, when Diameter of particles/droplets is selected, computed from the diameter of

particles and droplets dd:

 d0
n = 6 ---------3-
d d

DISPERSED PHASE OUTLET

This is the default for the Outlet node. This boundary condition is appropriate for
boundaries where the dispersed phase leaves the domain with the dispersed phase
velocity ud. No condition is imposed on the volume fractions at the boundary.

A corresponding flux condition is also applied for the number density equation (when
Solve for interfacial area is selected under the Physical Model section).

DISPERSED PHASE FLUX

Using this boundary condition, specify the dispersed phase flux through the boundary:

–n   d ud  = Nd

Enter the Dispersed phase flux (SI unit: m/s) in the N  d field.

If Solve for interfacial area is selected under the Physical Model section, the number
density flux through the boundary is also specified:

– n   nu d  = N n d

SYMMETRY
This boundary condition, which is useful on boundaries that represent a symmetry line
for the dispersed phase, sets the dispersed phase flux through the boundary to zero:

n   d ud  = 0

A corresponding flux condition is also applied for the number density equation (when
Solve for interfacial area is selected under the Physical Model section).

THEORY FOR THE MIXTURE MODEL INTERFACE | 561

 NO DISPERSED FLUX
This is the default for the Wall node. This boundary condition represents boundaries
where the dispersed phase flux through the boundary is zero:

n   d ud  = 0

In the case of moving and , the dispersed flux through the boundary is:

n   d ud  = n   d j 

This implies that the flux, relative to the boundary motion, is zero. A corresponding
flux condition is also applied for the number density equation (when Solve for
interfacial area is selected under the Physical Model section).

Turbulence Modeling in Mixture Models

Turbulence modeling is particularly relevant for dilute flows, that is, for flows with a
low dispersed phase volume fraction. For dense flows, the mixture viscosity usually
becomes high. In such cases, the flow is laminar and no turbulence modeling is
necessary.

The Mixture Model, Turbulent Flow interfaces include the turbulence models
described in .

The turbulence must be accounted for in the calculation of the dispersed phase volume
fraction. This is accomplished by introducing a turbulent dispersion coefficient Dmd
(SI unit: m2/s) in Equation 7-62 as

T
D md = ----------
 T

where T is the turbulent particle Schmidt number (dimensionless). The particle

Schmidt number is usually suggested a value ranging from 0.35 to 0.7. In the physics
interface the default value is 0.35. The so-called drift velocity is included in
Equation 7-62 as a diffusion term

    + j   +    j  m dc 
slip =    D md  d  – -------------
-
t d d d c

Similarly, the number density equation (used to compute the interfacial area) for
turbulent flow corresponds to

562 | CHAPTER 7: FLUID FLOW INTERFACES

 n
+ j  n +    n c u slip  =    D md n  – nm dc  ----- – ------
1 1
t   c  d

The inclusion of the drift velocity in Equation 7-62 modifies the flux of the dispersed
phase. The effective dispersed phase flux jd,eff and velocity ud,eff are given by

j d, eff = j d – D md  d

D md
u d, eff = u d – ------------  d
d

jd,eff and ud,eff are available in the physics interface as mm.jdEff and mm.udEff.

Slip Velocity Models

The Mixture Model interfaces contain three predefined models for the relative velocity
between the two phases uslip (SI unit: m/s):

• The Schiller-Naumann model

• The Haider-Levenspiel model
• The Hadamard-Rybczynski model

All three models use the following relation for the slip velocity:

C   – d  
- – j –  j   j + g + ----
3 F
--- ------d- u slip u slip = – ------------------- (7-65)
4 dd c  t 

where Cd (dimensionless) is the particle drag coefficient. Essentially, interpret the

relation as a balance between viscous drag and buoyancy forces acting on the dispersed
phase.

The Schiller-Naumann model models the drag coefficient according to

 24- 0.687
 ---------  1 + 0.15Re p  Re p  1000
Cd =  Re p

 0.44 Re p  1000

where Rep is the particle Reynolds number

d d  c u slip
Re p = ---------------------------


THEORY FOR THE MIXTURE MODEL INTERFACE | 563

 Note that this definition of the particle Reynolds number uses the viscosity of the
mixture and not the viscosity of the continuous phase, as would be customary for a
single particle in a pure fluid with viscosity c. This choice incorporates the hindrance
effect of the other particles on the slip velocity, see Ref. 17.

Because the particle Reynolds number depends on the slip velocity, an implicit
equation must be solved to obtain the slip velocity. Therefore, the Mixture Model
interfaces add an additional equation for

2
u slip

when the Schiller-Naumann slip model is used. The Schiller-Naumann model is

particularly well-suited for solid particles in a liquid.

The Haider-Levenspiel model is applicable to nonspherical particles. It models the

drag coefficient according to

B  Sp  C  Sp 
C d = ----------  1 + A  S p Re p  + ----------------------------------------
24
-
Re p  1 + D  S p   Re p

where A, B, C, and D are empirical correlations of the particle sphericity. The sphericity
is defined as the ratio of the surface area of a volume equivalent sphere to the surface
area of the considered nonspherical particle

A sphere
0  S p = ------------------  1
A particle

The correlation coefficients are given by

2.3288-6.4581S p + 2.4486S p2
A  Sp  = e
B  S p  = 0.0964+0.5565S p
4.905-13.8944S p + 18.4222S p2 – 10.2599S p3
C  Sp  = e
1.4681 + 12.2584S p – 20.7322S p2 + 15.8855S p3
D  Sp  = e

The diameter used in the particle Reynolds number is that of the volume equivalent
sphere. The equation for the squared slip velocity is also added when the
Haider-Levenspiel slip model is used.

564 | CHAPTER 7: FLUID FLOW INTERFACES

The Hadamard-Rybczynski drag law is valid for particle Reynolds numbers less than
1, for particles, bubbles, and droplets. The drag coefficient for liquid droplets or
bubbles is

 2 c 
 1 + --3- ----- d
-
24 
C d = ----------  --------------------
Re p 
 1 + -----c- 
 d 

which yields the following explicit expression for the slip velocity

 c 
2 1 + ------ 
  –  d d d  d  
= – --------------------------- -------------------- – j t –  j   j + g + ----
F
u slip
18  2 c   
 1 + --- ------
 3  d

For solid particles, the slip velocity is given by

2
  –  d d d
u slip = – ---------------------------  – j t –  j   j + g + ----
F
18 

when Rep  1. For very small gas bubbles, the drag coefficient is observed to be closer
to the solid-particle value. This is believed to be caused by surface-active impurities
collecting on the bubble surface.

References for the Mixture Model Interfaces

1. M. Manninen, V. Taivassalo, and S. Kallio, On the Mixture Model for Multiphase
Flow, VTT Publications, 288, VTT Energy, Nuclear Energy, Technical Research
Center of Finland (VTT), 1996.

2. C. Crowe, M. Sommerfeld, and Y. Tsuji, Multiphase Flows with Droplets and

Particles, CRC Press, 1998.

3. M.S. Nigam, “Numerical Simulation of Buoyant Mixture Flows,” Int. Jour. of

Multi. Flow., vol. 29, pp. 983–1015, 2003.

4. M. Ungarish, Hydrodynamics of suspensions, Springer-Verlag, 1993.

THEORY FOR THE MIXTURE MODEL INTERFACE | 565

 Theory for the Euler-Euler Interface
The Euler–Euler Model interfaces are based on averaging the Navier–Stokes equations
for each present phase over a volume that is small compared to the computational
domain but large compared to the dispersed phase (particles, droplets, or bubbles).
The two phases, the continuous and the dispersed phase, are assumed to behave as two
continuous and interpenetrating fluids, and the physics interface solves one set of
momentum equations for each phase.

In this section:

• The Euler–Euler Model Equations

• Some Notes on Boundary Conditions
• Turbulent Two-Phase Flow Modeling
• References for the Euler–Euler Model Interfaces

The Euler–Euler Model Equations

MASS BALANCE
The following continuity relations hold for the continuous and dispersed phases
(Ref. 3):

    +     u  = m (7-66)
t c c c c c dc

 
   +     d  d u d  = – m dc (7-67)
t d d

Here  (dimensionless) denotes the phase volume fraction,  (SI unit: kg/m3) is the
density, u (SI unit: m/s) the velocity of each phase, and mdc is the mass transfer rate
from the dispersed to the continuous phase (SI unit: kg/(m3·s)). The subscripts c and
d denote quantities relating to the continuous and the dispersed and phase,
respectively. The following relation between the volume fractions must hold

c = 1 – d

Both phases are considered to be incompressible, in which case Equation 7-66 and
Equation 7-67 can be simplified as:

566 | CHAPTER 7: FLUID FLOW INTERFACES

  c m dc
+     c u c  = ---------- (7-68)
t c

 d m dc
+     d u d  = – ---------- (7-69)
t d

If Equation 7-69 and Equation 7-68 are added together, a continuity equation for the
mixture is obtained:

    d u d + u c  1 –  d   = m dc  ----- – ------
1 1
(7-70)
  c  d

In order to control the mass balance of the two phases, the Euler–Euler Model
interfaces solves Equation 7-69 together with Equation 7-70. Equation 7-69 is used
to compute the volume fraction of the dispersed phase, and Equation 7-70 is used to
compute the mixture pressure.

MOMENTUM BALANCE
The momentum equations for the continuous and dispersed phases, using the
nonconservative forms (see for example Ref. 3 or Ref. 9), are:


c c  u  + uc    uc  =
t c (7-71)
–  c p +  c    c +  c  c g + F m,c +  c F c + m dc  u int – u c 


d d  u  + ud    ud  =
t d (7-72)
–  d p +  d    d +  d  d g + F m,d +  d F d – m dc  u int – u d 

Here p (SI unit: Pa) is the mixture pressure, which is assumed to be equal for the two
phases. In the momentum equations the viscous stress tensor for each phase is denoted
by (SI unit: Pa), g (SI unit: m/s2) is the vector of gravitational acceleration, Fm
(SI unit: N/m3) is the interphase momentum transfer term (that is, the volume force
exerted on each phase by the other phase), F (SI unit: N/m3) is any other volume
force term, and u int is the interphase velocity (SI unit: m/s).

In these equations, the influence of surface tension in the case of liquid phases has been
neglected, and the potential size distribution of the dispersed particles or droplets is
not considered.

THEORY FOR THE EULER-EULER INTERFACE | 567

 For fluid-solid mixtures where  d »  c , Equation 7-72 is modified in the manner of
Enwald (Ref. 5)


d d  u  + ud    ud  =
t d (7-73)
–  d p – p s +  d  d g + F m,d +  d F d – m dc  u int – u d 

where ps (SI unit: Pa) is the solid pressure.

The fluid phases in the above equations are assumed to be Newtonian and the viscous
stress tensors are defined as

 c =  cm  u c +  u c  – ---    u c I
T 2
 3 

 d =  dm  u d +  u d  – ---    u d I
T 2
3

where  cm and  dm (SI unit: Pa·s) are the dynamic viscosity model of the respective
phase. Observe how the viscous terms in equation Equation 7-71 and Equation 7-72
appear with their volume fractions outside the divergence operators. The equations can
also be derived so that the terms read     c  c  and     d  d  instead (see for
example Ref. 4 or Ref. 5). It depends on exactly how the derivation is carried out.
formulation in Equation 7-71 and Equation 7-72 are so that the momentum equation
can be divided by  c and  d respectively as described below.

In order to avoid singular solutions when the volume fractions tend to zero, the
governing equations above are divided by the corresponding volume fraction. The
implemented momentum equation for the continuous phase is:

 F m,c m dc
 c (u c) +  c u c    u c  = – p +    c +  c g + ----------- + F c + ----------  u int – u c 
t c c

The implemented momentum equations for the dispersed phase in the case of
dispersed liquid droplets or bubbles is:


d  u  + ud    ud  =
t d
(7-74)
F m,d m dc
– p +    d +  d g + ------------ + F d – ----------  u int – u d 
d d

568 | CHAPTER 7: FLUID FLOW INTERFACES

and in the case of dispersed solid particles:


d  u  + ud    ud  =
t d
(7-75)
p s F m,d m dc
– p – --------- +  d g + ------------ + F d – ----------  u int – u d 
d d d

VISCOSITY MODELS
The Newtonian viscosities of interpenetrating media are not readily available. Instead
empirical and analytical models for the dynamic viscosity of the two-phase mixture
have been developed by various researchers, usually as a function of the dispersed
volume fraction. Using an expression for the mixture viscosity, the default values for
the dynamic viscosities of the two interpenetrating phases are taken to be:

 cm =  dm =  mix (7-76)

A simple mixture viscosity covering the entire range of particle concentrations is the
Krieger type model (Ref. 5):

 d – 2.5 d,max
 mix =  c  1 – --------------- (7-77)
  d,max

Here  d,max is the maximum packing limit, by default 0.62 for solid particles.
Equation 7-77 can be applied when  c «  d . An extension of Equation 7-77 can be
applied for liquid droplets/bubbles:

 d + 0.4 c
– 2.5 d,max -------------------------
-
d d + c
 mix =  c  1 – --------------- (7-78)
  d,max

For liquid droplets/bubbles the default value of  d,max is 1.

For fluid-fluid systems, the simple relation

 mix =  c  c +  d  d (7-79)

can sometimes be applied or the viscosity for each individual phase can be applied to
the respective momentum equation.

An alternative to mixture viscosity for dispersed solid particles, that is particles in gas
flow, is to model the particle interface with a solid pressure instead (see Solid Pressure).

THEORY FOR THE EULER-EULER INTERFACE | 569

 A small viscosity is however necessary for numerical robustness and Gidaspow (Ref. 6)
suggested to use

 dm = 0.5max   d  d,res  (7-80)

This is consistent with the requirement that  dm  0 when  d  0 (Ref. 9), but in
practice it can suffice with any small enough, nonzero value.

INTERPHASE MOMENTUM TRANSFER

In all the equations, Fm denotes the interphase momentum transfer, that is the force
imposed on one phase by the other phase. Considering a particle, droplet, or bubble
in a fluid flow, it is affected by a number of forces, for example, the drag force, the
added mass force, the Basset force, and the lift force. The most important force is
usually the drag force, especially in fluids with a high concentration of dispersed solids,
and hence this is the predefined force included in the Euler–Euler model. The drag
force added to the momentum equation is defined as:

ꞏ
F drag,c = – F drag,d = u slip (7-81)

where  is a drag force coefficient and the slip velocity is defined as

u slip = u d – u c

The drag force on the dispersed phase is equal to the one on the
continuous phase but is working in the opposite direction.

The drag force coefficient, , is for solid particles often written as (Ref. 2)

3
 = ----------  d C D  c u slip (7-82)
4d d

For fluid-fluid system, Equation 7-82 is regularized to read (Ref. 12)

3
 = ----------  d  c C D  c u slip (7-83)
4d d

which is consistent with a vanishing  if  c  0 . All drag force models except

Gidaspow are based on Equation 7-82 for solid particles and on Equation 7-83 for
bubbles and droplets.

570 | CHAPTER 7: FLUID FLOW INTERFACES

Gidaspow
For dense particle flows with a high concentration of the dispersed phase — for
example, in fluidized bed models — the Gidaspow model (Ref. 6) for the drag
coefficient can be used. It combines the Wen and Yu (Ref. 7) fluidized state expression:

For  c > 0.8

3 c  d  c C d – 2.65
 = ---------------------------- u slip  c (7-84)
4d d

with the Ergun (Ref. 8) packed bed expression:

For  c < 0.8

2
c d d c
 = 150 -----------2- + 1.75 ----------- u slip (7-85)
c dd dd

In the above equations, dd (SI unit: m) is the dispersed particle diameter, and Cd is the
drag coefficient for a single dispersed particle. The drag coefficient is in general a
function of the particle Reynolds number

d d  c u slip
Re p = --------------------------
c

No universally valid expression for the drag coefficient exists. Using the implemented
Gidaspow model, Cd is computed using the Schiller-Naumann relation.

Schiller-Naumann
The Schiller-Naumann model describes the drag coefficient in Equation 7-82 and
Equation 7-83 for a single rigid sphere (see for example Ref. 3)

 24- 0.687
 ---------  1 + 0.15Re p  Re p  1000
Cd =  Re p (7-86)

 0.44 Re p  1000

It is valid for particle Reynolds numbers up to some critical Reynolds number,

approximately equal to 2.5·105 where drag crisis occurs.

The Schiller-Naumann model is appropriate for diluted flows since the correlation in
Equation 7-86 is based on a single particle and does not take particle-particle
interaction into account.

THEORY FOR THE EULER-EULER INTERFACE | 571

 The Schiller-Naumann model can be applied to small fluid particles since they do not
deform significantly.

Hadamard-Rybczynski
The Hadamard-Rybczynski drag law is valid for dilute flows with particle Reynolds
number less than one for particles, bubbles, and droplets and is defined as:

 2 c 
 1 + --3- ----- d
-
C d = ----------  --------------------
24
Re p 
 1 + -----c- 
 d 

for bubbles and droplets and as

24
C d = ----------
Re p

for solid particles (the Stokes limit). For very small gas bubbles, the drag coefficient is
observed to be closer to the solid-particle value. This is believed to be caused by
surface-active impurities collecting on the bubble surface.

Ishii-Zuber
The Ishii-Zuber model (Ref. 10) can for solid particles be regarded as a generalization
of the Schiller-Naumann model. For solid particles it can be formulated as

 24 1 + 17.67f   d  6 / 7 
C D = max  -----------  1 + 0.1Re m
0.75  0.45 ----------------------------------------------  (7-87)
 Re m 18.67f   d  

where

f  d  = c  c  m  (7-88)

and Rem is a Reynolds number based on the mixture viscosity

d d  c u slip
Re m = -------------------------- (7-89)
m

The Ishii-Zuber model is formulated with the assumption that  m is described by a

Krieger type model (Equation 7-77 for solids or Equation 7-78 for droplets and
bubbles). The dependence on  m means that the Ishii-Zuber model is valid also for
dense suspensions.

572 | CHAPTER 7: FLUID FLOW INTERFACES

For bubbles and droplets, Ishii and Zuber identifies three regimes. At low Reynolds
numbers, bubbles and droplets behave in the same way as solid particles and the drag
coefficient can be described by

24
C D visc = -----------  1 + 0.1Re m
0.75  (7-90)
Re m

When the Reynolds number becomes higher, bubbles and droplets start to deform in
such a way that the drag coefficient increases linearly with diameter but is independent
of viscosity. Ishii and Zuber refer to this as the distorted particle regime and suggest
the following correlation for this regime:

2 1 + 17.67f   d  6 / 7
C D dist = --- Eo ---------------------------------------------- (7-91)
3 18.67f   d 

where Eo is the Eötvös number

g  c –  d d d2
Eo = ------------------------------- (7-92)


where in turn g is the gravitational constant and  is the surface tension coefficient.
The Eötvös number relates surface tension forces to gravitational forces. The second,
“distorted” regime ends when hydrodynamic instabilities prevents the drag from
increasing further and the distorted regime is capped by the following value:

8
C D cap = ---  c2 (7-93)
3

The complete model for bubbles and droplets can hence be written:

 C D visc if C D visc  C D dist

CD =  (7-94)
 min  C
 D dist C D cap  if C D visc  C D dist

Haider-Levenspiel
The Haider-Levenspiel model is applicable to dilute flows with nonspherical solid
particles. It models the drag coefficient according to

B  Sp  C  Sp 
C d = ----------  1 + A  S p Re p  + ----------------------------------------
24 -
Re p   1 + D  S p   Re p

THEORY FOR THE EULER-EULER INTERFACE | 573

 where A, B, C, and D are empirical correlations of the particle sphericity (see for
further details).

Tomiyama et al.
The Tomiyama et al. (Ref. 11) provided three correlations for diluted bubbles and
droplets. The correlation for purified fluids read

 16 48 8 Eo 
C D = max  min ---------  1 + 0.15Re p0.687  ---------  --- -----------------  (7-95)
 Re p Re p 3 Eo + 4 

Fluid pure enough for Equation 7-95 to be valid is typically only achievable in
laboratory environments. Even small amounts of surface-active impurities can collect
at the droplet/bubble interface and cause a surface tension gradient which resists
surface movement. The correlation for slightly contaminated fluids therefore prescribe
a slightly higher drag coefficient:

 24 72 8 Eo 
C D = max  min ---------  1 + 0.15Re p0.687  ---------  --- -----------------  (7-96)
 Re p Re p 3 Eo + 4 

This correlation is the default one and applies to droplets and bubbles in fluids of
contamination levels comparable to ordinary tap water.

When the contamination level is high, the impurities effectively prevent all motion
within the droplet or bubble and the following correlation is suggested:

 24 8 Eo 
C D = max  min ---------  1 + 0.15Re p0.687  --- -----------------  (7-97)
 Re p 3 Eo + 4 

SOLID PRESSURE
For fluid-solid mixtures where  d »  c , for example solid particles in gas flow, a model
for the solid pressure, ps in Equation 7-75, is needed. The solid pressure models the
particle interaction due to collisions and friction between the particles. The solid
pressure model implemented uses a gradient diffusion based assumption:

p s = – G   c  c

where the empirical function G can be though of as a modulus of elasticity or powder

modulus. A common form for G is (Ref. 5)

B1 c + B2
G   c  = 10 (7-98)

574 | CHAPTER 7: FLUID FLOW INTERFACES

The available predefined models (all defined in Ref. 5) are those of Gidaspow and
Ettehadieh,

-8.76 c + 5.43
G   c  = 10 (7-99)

Ettehadieh,

-10.46 c + 6.577
G   c  = 10 (7-100)

and Gidaspow,

-10.5 c + 9.0
G   c  = 10 (7-101)

Observe that the solid pressure term theoretically replaces the stress term in the
dispersed phase momentum equation. A small viscosity is however necessary for
numerical robustness. The Gidaspow formulation or a small constant value is
appropriate. The viscosity for the continuous phase,  cm , can be taken as the single
phase value, that is  cm =  c .

NOTES ON THE IMPLEMENTATION

There are several equations with potentially singular terms and expressions such as the
term

F m,d
------------
d

in Equation 7-74. Also,  d is a degree of freedom and can therefore, during

computations, obtain nonphysical values in small areas. This can, in turn, lead to
nonphysical values of material properties such as viscosity and density. To avoid these
problems, the implementation uses the following regularizations:

• 1  k, kc,d is replaced by1  k,pos where

 k pos = max   k  k,res 

The residue volume fractions are per default set to 104 but can be changed in the
section of the interface settings.
• When appropriate, for example when evaluating drag models and mixture
viscosities,  k, kc,d are replaced by

THEORY FOR THE EULER-EULER INTERFACE | 575

  k reg = min  max   k 0  1 

Note however that the continuity equation, Equation 7-70, uses  k without
regularization in order to guarantee mass conservation.

Some Notes on Boundary Conditions

An effect of dividing the momentum equations with  c and  d respectively is that for
example ud obtains a value even if  d = 0 . In many cases ud will tend to uc in lack of
a dispersed phase. So on inlets where  d = 0 , it is appropriate to set uduc.

A fixed value for  d should only be prescribed if there is no transport of  d toward

the inlet. If, for example, a cloud of dispersed phase with higher  d than the prescribed
value somehow reaches the inlet,  d will actually be “consumed”.

When specifying a dispersed phase flux, make sure to specify an appropriate velocity to
go with the flux to avoid nonphysical concentrations of  d close to the boundary.

At walls, where it is possible to prescribe a wall leakage, the continuous phase normal
velocity is set to

ꞏ
mc
u c  n = – --------------------
 c  c pos

For a dispersed phase leakage:

 ꞏ
 md ꞏ
 – --------------------------------- if  m d  0 
  d  1 –  c res 
ud  n = 
 ꞏ ꞏ
 mc if  m d  0 
 – ---------------------
 d  d pos


That is, dispersed phase is injected with a low velocity and transported out with a
velocity that is consistent with the specified flux. Wall leakage for one phase works best
if combined with slip condition for the other phase so that the mixture is given
maximum freedom to react to the leakage.

576 | CHAPTER 7: FLUID FLOW INTERFACES

Turbulent Two-Phase Flow Modeling
When the characteristic Reynolds number of the two-phase mixture under
investigation becomes high, the flow transitions and becomes turbulent. The influence
of the turbulence on the flow characteristics (mixing, particle dispersion, pressure
drop, and so on) are usually significant and warrants the use of a turbulence model.

In order to model fluid flow turbulence, the Euler–Euler Model, Turbulent Flow
interface uses the k- turbulence model. This is realized by solving transport equations
for the kinetic energy k (SI unit: m2/s2) and the dissipation rate of turbulent kinetic
energy  (SI unit: m2/s3).

The interface includes the possibility to model the turbulent flow of the two-phase
mixture, or to solve for turbulent flow of each phase separately. In the former case, one
set of k- equations are solved, while in the latter two sets of k- equations are solved
for, one for each phase.

MIXTURE TURBULENCE
Mixture turbulence assumes that the turbulence effects on both the continuous and
dispersed phase can be modeled by solving for the turbulence of the resulting
two-phase mixture. Here this is done using a two-equation k- model where the
transport of turbulence quantities is based on based on the mass-averaged mixture
velocity

c c um + d d um
u m = ----------------------------------------------- ,


and a volume-averaged mixture viscosity

 m =  c  cm +  d  dm

This implies that the model is appropriate for flows where the relaxation time of the
dispersed particles (the time scale on which particles react to changes in the carrier fluid
velocity) is not significantly different to the time scale of the turbulence. It is also
appropriate for stratified flows, where the mixture mainly consists of one of the phases.

Setting the Two-phase turbulence interface property to Mixture, the turbulence of the
two-phase flow is modeled by solving the following k and equations:

k T
 ------ +  u m  k =      m + ------ k + P k –  (7-102)
t    k 

THEORY FOR THE EULER-EULER INTERFACE | 577

  T  2
 ----- +  u m   =      m + ------  + C 1 --- P – C 2  ----- (7-103)
t     k k k

The equations correspond to the standard two-equation k- model including

realizability constraints.

The production term is defined accordingly as

P k =  T  u m :  u m +  u m  T  – ---    u m  2 – --- k  u m

2 2
 3  3

and the resulting turbulent viscosity is defined as

k2
 T = C  ------


where C is a model constant. The viscous stress tensors for the phases are hence
defined as

 c =   cm +  T   u c +  u c  – ---    u c I – ---  c kI ,

T 2 2
3 3

 d =   dm +  T   u d +  u d  – ---    u d I – ---  d kI .

T 2 2
 3  3

Assuming mixture turbulence, the transport equation for the volume fraction is:

 
  +     d u d  =    D md  d  (7-104)
t d

Here the dispersion of the particulate phase by the turbulent fluctuations is modeled
using a gradient based hypothesis. The turbulent dispersion coefficient is defined from
the turbulent viscosity of the two-phase mixture in the manner of

T
D md = ----------
 T

where T is a turbulent particle Schmidt number (dimensionless).

578 | CHAPTER 7: FLUID FLOW INTERFACES

The default values of the dimensionless parameters using the Mixture Two-phase
turbulence model are:

CONSTANT VALUE

C 0.09
C1 1.44
C2 1.92
k 1.0
 1.3
Kv 0.41
B 5.2
 0.35

PHASE SPECIFIC TURBULENCE

The phase specific Two-phase turbulence model assumes that the turbulent flow of the
continuous and dispersed phase can be modeled by solving for the turbulence of each
phase separately by using two sets of k- equations. The model implies that the time
scales of the turbulent flow of each phase can differ, but it is also computationally more
expensive than assuming solving one set of k- equations for the mixture.

Setting the Two-phase turbulence interface property to Phase specific, the turbulent flow
of the two phases is modeled by solving two sets of k and equations, one for each
phase. For the continuous phase, the transport equations for k and are

k c  T,c
 c -------- +  c u c  k c =      cm + ---------- k c + P k c –  c  c (7-105)
t   k c 

 c  T,c c  d2
 c ------- +  c u c   c =      cm + ----------  c + C 1,c ----- P k c – C 2,c  ------ (7-106)
t    c kc kd

while for the dispersed phase the corresponding equations are

k d  T,d
 d --------- +  d u d  k d =      dm + ----------- k d + P k d –  d  d (7-107)
t   k d 

 d  T,d d  d2
 d -------- +  d u d   d =      dm + ----------  d + C 1,d ------ P k d – C 2,d  ------ (7-108)
t    d  kd kd

THEORY FOR THE EULER-EULER INTERFACE | 579

 The equations for each phase correspond to the standard two-equation k- model
including realizability constraints.

The production terms are defined as

P k c =  T,c  u c :  u c +  u c  T  – ---    u c  2 – ---  c k d   u c

2 2
3 3

P k d =  T,d  u d :  u d +  u d  T  – ---    u d  2 – ---  d k d   u d

2 2
3 3

The resulting turbulent viscosity, applied individually in the momentum equations of

the continuous and the dispersed phases, are

k c2 k d2
 T c =  c C  c ------ ,  T d =  d C  d ------ (7-109)
c d

where Cc and Cd are model constants. The viscous stress tensors for the phases are
hence defined as

 c =   cm +  T c   u c +  u c  – ---    u c I – ---  c k c I ,

T 2 2
 3  3

 d =   dm +  T d   u d +  u d  – ---    u d I – ---  d k d I .

T 2 2
3 3

As in the case of mixture turbulence, the dispersion of the particulate phase by the
turbulent fluctuations is modeled using a gradient based hypothesis (Equation 7-104).
For phase-specific turbulence the dispersion coefficient is modeled as a volume average
of the respective turbulent diffusivity of each phase

 T c  T d
D md = -----------   c ----------- +  d -----------
1
 T d c d

using a turbulent particle Schmidt number T,d (dimensionless).

580 | CHAPTER 7: FLUID FLOW INTERFACES

The default values of the turbulence model parameters for phase specific turbulence are

CONTINUOUS VALUE DISPERSED VALUE

PHASE PHASE
CONSTANTS CONSTANTS

Cc 0.09 Cd 0.09

C1c 1.44 C1d 1.44
C2c 1.92 C2d 1.92
kc 1.0 kd 1.0
c 1.3 d 1.3
Kv,c 0.41 Kvd 0.41
Bc 5.2 Bd 5.2
d 0.35

References for the Euler–Euler Model Interfaces

1. M.J.V. Goldschmidt, B.P.B. Hoomans, and J.A.M. Kuipers, “Recent Progress
Towards Hydrodynamic Modelling of Dense Gas-Particle Flows”, Recent Research
Developments in Chemical Engineering, Transworld Research Network, India, pp.
273–292, 2000.

2. M. Ishii and T. Hibiki, “Thermo-Fluid Dynamics of Two-Phase Flow”, Springer

US, 2006.

3. C. Crowe, M. Sommerfeld, and Y Tsuji, Multiphase Flows with Droplets and

Particles, CRC Press, Boca Raton, 1998.

4. B.G.M. van Wachem, J.C. Schouten, C.M. van den Bleek, R. Krishna, and J.L.
Sinclair, “Comparative Analysis of CFD Models of Dense Gas-Solid Systems”, AIChE
Journal, vol. 47, no. 5, pp. 1035–1051, 2001.

5. H. Enwald, E. Peirano, and A.-E. Almstedt, “Eulerian Two-Phase Flow Theory

Applied to Fluidization”, Int. J. Multiphase Flow, vol. 22, pp. 21–66, 1996.

6. D. Gidaspow, Multiphase Flow and Fluidization, Academic Press, San Diego,

1994.

7. C.Y. Wen and Y.H. Yu, “Mechanics of Fluidization”, Chemical Engineering

Progress Symposium Series, vol. 62, pp. 100–110, 1966.

8. S. Ergun, “Fluid Flow Through Packed Columns”, Chemical Engineering

Progress, vol. 48, pp. 89–94, 1952.

THEORY FOR THE EULER-EULER INTERFACE | 581

 9. M. Ungarish, Hydrodynamics of Suspensions, Springer-Verlag, 1993.

10. M. Ishii and N. Zuber, “Drag Coefficient and Relative Velocity in Bubbly, Droplet
or Particulate Flows”, AIChE Journal, vol. 25, no. 5, 1979.

11. A. Tomiyama, I. Kataoka, I. Zun and T. Sakaguchi, “Drag coefficients of single

bubbles under normal and micro gravity conditions”, JSME International Journal,
series B. Vol. 41, pp. 472–479, 1998.

12. P.J. Oliveira and R.I. Issa, “Numerical aspects of an algorithm for the Eulerian
simulation of two-phase flows”, Int. J. Numer. Meth. Fluids, vol. 43, pp. 1177–1198,
2003.

582 | CHAPTER 7: FLUID FLOW INTERFACES

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 = ---
  ni  n (7-110)
i

where (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 = –  ---
  Mi Ni n (7-111)
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:

-
-----
t
+    u  =  Ri mass (7-112)
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.

THEORY FOR THE COUPLING OF FLUID FLOW TO ELECTROCHEMICAL REACTIONS | 583

584 | CHAPTER 7: FLUID FLOW INTERFACES
 8

Heat Transfer Interfaces

As with all other physical descriptions simulated by COMSOL Multiphysics, any

description of heat transfer can be directly coupled to any other physical process.
This is particularly relevant for systems based on chemical reactions and mass
transfer along with fluid flow. These physics interfaces are found under the Heat
Transfer branch ( ).

The basic functionality for simulating heat transfer in homogeneous media is

described in The Heat Transfer Interfaces in the COMSOL Multiphysics Reference
Manual.

The Fuel Cell & Electrolyzer 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 Fuel Cell & Electrolyzer Module irrespectively of
whether a separate Heat Transfer Module license is purchased.

In this chapter:

• Coupling of Heat Transfer to Electrochemical Reactions

585
 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 xxx.Qh
(domain, Joule heating and porous electrode reactions) and xxx.Qbfc (boundary,
electrode surface reactions), where xxx is the electrochemistry interface identifier.

• Electrochemistry Interfaces
• Multiphysics Coupling Nodes

586 | CHAPTER 8: HEAT TRANSFER 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   s + i l   l  (8-1)

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

H m G m
Q m =  ------------- –  ------------- –  m tot  i m (8-2)
nm F nm F

where Hm is the enthalpy change of the reaction, and Gm is the Gibbs free energy
of the reaction, Gm, defined as

G m = H m – TS m

where Sm is the net entropy change. The equilibrium potential is related to Gm in
the following way:

G m
E eq m = – -------------
nm F

In Equation 8-2 we have used the total overpotential, m,tot,(including potential

effects from film resistances and similar), defined as

 m tot =  s –  l – E eq m

By the relation

E eq m S m
------------------
- = -----------
-
T nm F

the local heat source due to the electrochemical conversion process becomes

COUPLING OF HEAT TRANSFER TO ELECTROCHEMICAL REACTIONS | 587

 E eq m
Q m =   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

 a m F m –  c m F m
i loc m = i 0 m  C R m exp  ------------------------- – C O m exp  ---------------------------- 
RT RT

where

 m =  s –  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.

588 | CHAPTER 8: HEAT TRANSFER INTERFACES

When using the Concentration Dependent kinetics option, the overpotential, used in
the irreversible heat term above, is calculated as follows:

 m tot =  s –  l – E eq m +  m conc

where

RT C O m
 m conc = ------------ ln --------------
n m F C R m

If the number of electrons is not available,

nm =  ꞏ +  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 | 589

590 | CHAPTER 8: HEAT TRANSFER INTERFACES
 9

Thermodynamics

This chapter describes how you can use the thermodynamics functionality to
define thermo-physical and transport properties. The properties in turn can be used
when simulating chemical reaction systems, or any type of transport model
involving mass transfer, fluid flow, or heat transfer.

In this chapter:

• Using Thermodynamic Properties

• Thermodynamic Models and Theory

591
 Using Thermodynamic Properties
In this section:

• Workflow for Thermodynamics Property Calculations

• Thermodynamics
• Thermodynamic System
• External Thermodynamic Packages
• External Thermodynamic System
• Predefined System
• Exporting and Importing Thermodynamic Systems
• Species Property
• Mixture Property
• Equilibrium Calculation
• Generate Chemistry
• Generate Material
• Coupling with the Reaction Engineering and the Chemistry Interfaces
• Evaluating a Property Function in a Physics Interface
• User-Defined Species
• References

Workflow for Thermodynamics Property Calculations

The thermodynamic properties database, together with the thermodynamic calculator,
make it possible to evaluate physical properties of fluids such as heat capacity, thermal
conductivity, density and diffusivity, as well as equilibrium compositions of two phases
at equilibrium. The properties can be calculated for pure fluids, mixtures, and for
two-phase fluid systems consisting of pure species as well as mixtures.

Using the thermodynamics functionality involves the following main steps:

592 | CHAPTER 9: THERMODYNAMICS

1 Add the Thermodynamics node and create a thermodynamic system to add properties
for a selected set of chemical compounds, referred to as chemical species in this
manual. A thermodynamic system can be created in the following ways:
- A built-in Thermodynamic System uses the built-in, or user-defined, property
database with native functionality for thermodynamic property calculations.
- An External Thermodynamic System uses properties from an installed external
package provider. For more information on how to enable the use of external
packages see the Installing External Thermodynamic Packages — An Example.
- A Predefined System uses the built-in database with native functionality to set up
one of the following common systems; Dry air, Moist air, or Water-steam.

2 Once a thermodynamic system is set up, it can be used to define a multitude of

property functions. The Generate Material option provides a fast route to defining
the material properties most commonly required for fluid flow, heat transfer and
mass transfer modeling. By specifying the composition and phase of the mixture, a
Material node can automatically be set up. The material node can include properties
such as density, heat capacity, heat capacity ratio, thermal conductivity and viscosity.
3 Users of the Reaction Engineering, or Chemistry interface can couple chemical
species in these interfaces with the chemical species in the thermodynamic system.
When Coupling with the Reaction Engineering and the Chemistry Interfaces the
required property parameters and functions are automatically added and visualized
as nodes under the corresponding thermodynamic system node.
4 As an alternative to the functions automatically set up when using Generate Material
or coupling to e.g. Chemistry, functions or constants can be set up manually for any
thermodynamic system. This is accomplished using the thermodynamic features
Species Property, Mixture Property or Equilibrium Calculation. You can, for
example, create a Species Property function describing the density of a fluid, and use
this function in a fluid-flow interface. With Mixture Property you can define mixture
functions, i.e. functions that depend on the composition of a mixture, describing for
example density, enthalpy, or heat capacity.

The functionalities described in Step 2- 4 generate functions and constants, defined by

a thermodynamic system, that can be used in any physics interface in COMSOL
Multiphysics. The functions are used to evaluate fluid properties that depend on
variables such as temperature, pressure, and mixture composition. For more
information, see Evaluating a Property Function in a Physics Interface.

USING THERMODYNAMIC PROPERTIES | 593

 Thermodynamics
To access the functionality for thermodynamic calculations, right-click the Global
Definitions node in the Model Builder tree and select Thermodynamics ( ). Using the
Reaction Engineering or Chemistry interfaces, Thermodynamics is also available on the
Reaction Engineering or Chemistry toolbar.

Figure 9-1: The Thermodynamics feature available under Global Definitions.

Thermodynamic properties given as parameters or functions are collected in a so called

thermodynamic system. Each thermodynamic system includes a set of available species
and phases, as well as different models used for the thermodynamic property
calculations, for example an equation of state such as Peng-Robinson.

Select Thermodynamic System in the context menu to add a thermodynamic system

that uses the database included in the Liquid & Gas Properties Module.

As an alternative, selecting External Thermodynamic System can make use of an

installed thermodynamics software to make the corresponding calculations.

The option Predefined System, allows you to set up one of the following systems; Dry
air, Moist air, or Water-steam.

It is also possible to import previously created and stored thermodynamic systems by

selecting Import Thermodynamic System (see Exporting and Importing
Thermodynamic Systems).

594 | CHAPTER 9: THERMODYNAMICS

In addition to creating thermodynamic systems, you can also define User-Defined
Species in Thermodynamics. Use User-Defined Species to add new species that are not
available in COMSOL database. You can also edit available species in the database.

Figure 9-2: Adding Thermodynamic Systems to the Thermodynamics node. Note that
external package providers have been installed.

When a thermodynamic system has been added, thermodynamic and transport

properties are defined by functions. These can be used to describe properties for pure
species, mixtures, and for gas-liquid (or liquid-liquid) systems at equilibrium.

Thermodynamic System
A thermodynamic system is used to describe properties of pure species and mixtures of
chemical compounds for liquids, gases, liquid-vapor equilibria, and liquid-liquid
equilibria. It specifies the available species and the phases (states of aggregation) that
are present in the modeled system. It also defines and evaluates the functions for
thermodynamic and transport properties of the chemical system, that is, the species
and mixture properties for liquids, gases and phase equilibria.

USING THERMODYNAMIC PROPERTIES | 595

 To create a Thermodynamic System, start the Thermodynamic System Wizard in one of
the following ways:

• Right-click the Global Definitions node, select Thermodynamics and choose

Thermodynamic System.
• Using the Reaction Engineering interface, choose Thermodynamic System from the
Thermodynamics section of the Reaction Engineering toolbar.

• Correspondingly, using the Chemistry interface, choose Thermodynamic System

from the Thermodynamics section of the Chemistry toolbar.

The Thermodynamic System Wizard contains the following steps:

1 Select System
2 Select Species
3 Select Thermodynamic Model

SELECT SYSTEM
Use the Select System step in the wizard to define the phases in the modeled system.
You can select Gas, Liquid, Vapor-liquid, Vapor-liquid-liquid, or Liquid-liquid. The names
of the phases in the Selected system table can be changed by editing the element in the
Name column. Click the Next button ( ) to proceed to the next step in the wizard.

Figure 9-3: Thermodynamic System Wizard: Select System.

SELECT SPECIES
Use the Species Type filter text field to search among the available species in the COMSOL
database or the User-Defined Species. Species can be searched for by typing the name,
CAS number, or the chemical formula. Select one or more species in the list and click
the Add Selected button ( ) to add species to the Selected species table. To remove
species from the Selected species table, use either the Remove Selected button ( )

596 | CHAPTER 9: THERMODYNAMICS

or the Remove All button ( ), both located below the table. Click the Next button
( ) to proceed to the next step in the wizard.

Figure 9-4: Thermodynamic System Wizard: Select Species.

SELECT THERMODYNAMIC MODEL

The Thermodynamic model controls the relations between the intensive
thermodynamic properties of the system such as pressure, specific volume, and
temperature. It also controls how extensive properties like enthalpy, entropy, or the
heat capacity of the system are computed. Furthermore, the Thermodynamic model
specifies the default models used to compute transport properties.

The following Thermodynamic Models are available for all phases:

• Peng-Robinson
• Peng-Robinson (Twu)
• Soave-Redlich-Kwong
• Soave-Redlich-Kwong (Graboski-Daubert)

For a system including only gas phase, or for liquid phase systems with thermodynamic
models requiring an equation of state, the Ideal Gas Law is added to the available
models in the Gas phase model list or Equation of state list.

USING THERMODYNAMIC PROPERTIES | 597

 When the system includes one or more liquid phases, the following additional models
are also available (in the Liquid phase model list):

• Chao Seader (Grayson-Streed)

• Wilson
• NRTL
• UNIFAC VLE
• UNIQUAC
• Regular Solution
• Extended Regular Solution
• Ideal Solution

These models correspond to activity models.

To calculate properties of water and steam, use the Water (IAPWS) model. This is
available for systems that include a single water species.

For recommendations regarding the appropriate thermodynamic model, based on the

available phases and the system pressure level, see the section Selecting the Right
Thermodynamic Model.

Select the Advanced options check box in order to manually control the models used
for thermodynamic properties, transport properties, and surface tension. When this
check box is selected, all available property models are shown in the property model
table. The available property models are dependent on the phases available in the
thermodynamic system.

When only a gas phase is present, models are available for the following properties:

• Gas diffusivity
• Gas thermal conductivity
• Gas viscosity

For a single-phase liquid, or for a two-phase liquid-liquid system, there are models for
the following properties:

• Liquid diffusivity
• Liquid diffusivity at infinite dilution
• Liquid-liquid surface tension
• Liquid thermal conductivity

598 | CHAPTER 9: THERMODYNAMICS

• Liquid viscosity
• Liquid volume

For systems with both vapor and liquid phases, all of the above properties are available,
as well as Gas-liquid surface tension.

Figure 9-5: Thermodynamic System Wizard: Advanced thermodynamic model options

available for a Vapor-liquid system.

Click the Finish button ( ) to exit the Thermodynamic System Wizard and add the
corresponding system under the Thermodynamics node. Note that the default node
label reflects the available phase in the system. For example, when creating a
vapor-liquid system, a node labeled Vapor-Liquid System is added. The name of the
system can be changed using the Label text field in the Settings window for the system.

SETTINGS
Selecting a Thermodynamic System or Predefined System node shows its Settings
window with a description of the package content and the available properties. Editing

USING THERMODYNAMIC PROPERTIES | 599

 the text in the Label text field changes the name of the system. Below follows a
description of the thermodynamic system settings.

Figure 9-6: Thermodynamic System Settings.

Provider:
Contains information about the thermodynamic system such as the version it was
created in and the manager used to create it. For a built-in thermodynamic system, the
manager corresponds to COMSOL.

Species:
Lists the species included in the thermodynamic system. You can change the list of
species by right-clicking the Thermodynamic System node and selecting Add or Remove
Species.

Phases:
Lists the phases included in the thermodynamic system. You can add or remove phases,
such as gas, liquid or liquid-vapor, by right-clicking the Thermodynamic System node
and selecting Define System.

600 | CHAPTER 9: THERMODYNAMICS

Species Property:
Lists the parameters and functions that describe thermodynamics and transport
properties for pure species. Such functions may describe density, heat capacity, thermal
conductivity, or other thermodynamic and transport properties. For more
information, see Species Property.

Mixture Property:
Lists the available mixture property functions. Note that you have to have a mixture
model defined in order to use these functions. You can define a mixture property by
right-clicking the Thermodynamic System node and selecting Mixture Property.

Thermodynamic Model:
When a liquid is present, use the Liquid phase model list to select the thermodynamic
model for this phase.

When a gas is present, use the Gas phase model list to select the thermodynamic model
for this phase. If also a liquid phase is available, and the Liquid phase model corresponds
to an equation of state, then the Gas phase model is set to the same model.

Property Models:
Displays the settings for the available individual property models. The property models
can be changed by selecting different values from the combo box in the Model
column. For example, for Gas thermal conductivity you can select Kinetic theory or Ideal
from the corresponding combo box. You can also select the property model in the last
step of the thermodynamic system wizard by selecting the Advanced option check box,
see Select Thermodynamic Model.

Binary Interaction Parameters:

This section can be used to inspect and edit binary interaction parameters. Select a pair
of species (first and second column, Species 1 and Species 2) as shown in Figure 9-7
to edit the corresponding binary interaction parameter currently in use. In cases that
the thermodynamic model has more than one type of binary interaction parameter,
each type of the interaction parameter will be shown in a column in the table.

Figure 9-7: Entering the Binary Interaction Parameters for the Soave-Redlich-Kwong
model.

USING THERMODYNAMIC PROPERTIES | 601

 When a binary interaction parameter is not available in the database for a pair of
species, the parameter value is set to zero (default value).

MODIFYING AN EXISTING SYSTEM

It is possible to modify an existing thermodynamic system, for example by changing
the included species or phases. To do so, right-click the Thermodynamic System node
and select Add or Remove Species, or Define System from the context menu. Both of
these options are available for systems created using Thermodynamic System. For a
Predefined System, the option Add or Remove Species is available for Dry Air and Moist
Air. For a Water-steam system, neither of the two options are available.

When the properties of a User-Defined Species has been changed, select Update From
Species for the changes to take effect in the thermodynamic system.

Figure 9-8: Modifying the species and phases of a thermodynamic system.

Add or Remove Species

Selecting Add or Remove Species takes you to the Select Species step in the
Thermodynamic System Wizard. Use the Add Species button ( ) to add a species to the
Selected Species list. To remove a species, select it in the list and use the Remove Species
button ( ).

Make sure to click the Finish button ( ) in order for the changes to take effect.

Note that adding or removing species in a thermodynamic system that is currently

coupled to a Reaction Engineering interface or a Chemistry interface breaks this
coupling. See the Coupling with the Reaction Engineering and the Chemistry
Interfaces for how to update this coupling.

602 | CHAPTER 9: THERMODYNAMICS

Define System
Selecting Define System takes you to the Select System step in the Thermodynamic
System Wizard. You can select the desired system from the list.

Make sure to click the Finish button ( ) button in order for the changes to take
effect.

Note that changing the phase(s) in a thermodynamic system that is currently coupled
to a Reaction Engineering interface or a Chemistry interface breaks this coupling. See
the Coupling with the Reaction Engineering and the Chemistry Interfaces section for
how this coupling can be updated.

Update From Species

This option is available in a Thermodynamic System that includes a User-Defined
Species. Use it to update the system following a change in the species properties.

WARNING INFORMATION
A sanity check is always performed when a Thermodynamic System is created. If any
problems are found, a Warning Information node listing the problems is added under
the package. One example when this occurs is when a parameter required for the
thermodynamic model, typically a binary interaction parameter, is not available in the
database.

External Thermodynamic Packages

The thermodynamics functionality includes support for creating properties from
external thermodynamic packages. In order to use external packages, the external
software has to be CAPE-OPEN compliant. The Liquid & Gas Properties Module
supports the CAPE-OPEN Thermo 1.1 and the CAPE-OPEN Thermo 1.0 standards.

CAPE-OPEN is an open interface standard for chemical process simulation software

(Ref. 1). This standard defines rules and interfaces that allows linking between
compliant software. Some examples of CAPE-OPEN compliant software are:

• COCO/TEA (Free of charge package provider; see Ref. 2).

• Multiflash™ (KBC Advanced Technologies plc).
• VMGThermo™ (Virtual Materials Group, Inc.).
• Simulis® Thermodynamics (ProsSim SA).
• Aspen Properties, aspenONE® (Aspen Technology, Inc.).
• COMThermo® packages (comes with Aspen HYSYS®).

USING THERMODYNAMIC PROPERTIES | 603

 Accessing external thermodynamic systems allows species properties, mixture
properties, as well as phases equilibrium calculations (gas-vapor, liquid-liquid) to be
obtained from external software, such as the ones listed above.

INSTALLING EXTERNAL THERMODYNAMIC PACKAGES — AN EXAMPLE

TEA is a thermodynamics thermodynamic system that handles the physical and
thermodynamic property calculations for the simulation environment COCO. The
property data bank contains of over 190 commonly used chemicals, and the package
exhibits more than 100 property calculation routines with their analytical or numerical
derivatives. COCO is maintained by AmsterCHEM and is free to download from the
Internet (Ref. 2).

To use the external physical and thermodynamic property calculations from

COCO/TEA in COMSOL Multiphysics models, you need to go through the
following steps:

1 Download and install COCO, which includes the TEA thermodynamic system
manager. The software is available from
www.cocosimulator.org/index_download.html.
2 Create and configure a thermodynamic system template that handles physical and
thermodynamics calculations needed for your model. If you have already created a
package template earlier, or if an adequate thermodynamic system already exists in
the installation, this step is not needed.
3 Create an External Thermodynamic System node as detailed in the next section.
The installed packages are available in the Select Property Package step of the
Thermodynamic System Wizard.

External Thermodynamic System

The following assumes that you have installed external thermodynamic packages from
a CAPE-OPEN compliant software in the manner outlined in Installing External
Thermodynamic Packages — An Example.

Locate the Thermodynamics node and right-click to add an External Thermodynamic

System (Figure 9-2). Using a Reaction Engineering or Chemistry interface, you can also
add an external package by choosing External Thermodynamic System from the
Thermodynamics section of the Reaction Engineering, or Chemistry, toolbar.

604 | CHAPTER 9: THERMODYNAMICS

SELECT PROPERTY PACKAGE
All installed packages, from providers such as COCO/TEA, Aspen Properties, etc, are
available in the Thermodynamic System Wizard (Figure 9-9). Select one of the packages
and click the Finish button ( ) in the upper right corner of the wizard in order to
add the package as an External Thermodynamic System node under the Thermodynamics
node.

When adding the package its default label reflects the included phases. For example, a
node labeled Vapor-Liquid System (External) is created when adding an external
package containing a vapor and a liquid phase. The name of the system can be changed
using the Label text field in the Settings window for the system.

Figure 9-9: Available external thermodynamic systems. Use the Thermodynamic System
Wizard to browse the contents of the installed external thermodynamic systems on your
system. The example shows the packages shipped with the COCO provider.

SETTINGS
Selecting the External Thermodynamic System node shows the thermodynamic system
settings with sections for available species, phases, species properties, and mixture
properties. Editing the text in the Label text field changes the name of the system.
Below follows a description of the thermodynamic system settings.

USING THERMODYNAMIC PROPERTIES | 605

 Provider
Contains information about the external thermodynamic system provider such as
version, CAPE-OPEN compliance, and a short description of the external software
that provides the thermodynamic system.

Species
Lists the species included in the selected thermodynamic system.

Phases
Lists the phases included in the selected thermodynamic system for example gas,
liquid, gas-vapor, or liquid-liquid.

Species Properties
Lists the parameter values or the functions that describe species properties, for example
molar mass, and properties available for pure compounds, such as density as a function
of temperature.

606 | CHAPTER 9: THERMODYNAMICS

Mixture Properties
Lists the available functions that describe mixture properties. One example is the
density of a nonideal mixture as a function of composition.

Figure 9-10: Settings window for an External Thermodynamic System.

The thermodynamic functionality supports package persistence. This

means that an mph-file for a model that uses a thermodynamic system
stores that package definition in the file. You can use the mph-file to
access a thermodynamic system defined in the corresponding model
without having to store the thermodynamic system as a separate file.

Predefined System
A Predefined System uses the built-in database with native functionality to set up one
of the following common systems; dry air, moist air, or water and steam.

USING THERMODYNAMIC PROPERTIES | 607

 To create a Predefined System, start the Thermodynamic System Wizard in one of the
following ways:

• Right-click the Global Definitions node, select Thermodynamics and choose Predefined
System.
• Using the Reaction Engineering interface, choose Predefined System from the
Thermodynamics section of the Reaction Engineering toolbar.

• Correspondingly, using the Chemistry interface, choose Predefined System from the
Thermodynamics section of the Chemistry toolbar.

The Thermodynamic System Wizard that opens is identical to the wizard used to create
a Thermodynamic System, but with the important difference that all settings have been
entered for the chosen predefined system. The wizard contains the following steps:

1 Select System
2 Select Species
3 Select Thermodynamic Model

SELECT SYSTEM
In the Select System window, choose one of the predefined systems in the list. Choose
among Dry air, Moist air and Water-steam. Click the Next button ( ) to proceed to
the next step in the wizard.

Figure 9-11: Thermodynamic System Wizard: Select Predefined System.

SELECT SPECIES
If Dry or Moist air was chosen in the Select System step, the Selected species table is
populated with the species relevant for the chosen system. For Dry air the species are:
nitrogen, oxygen, argon, carbon dioxide, neon and helium. For Moist air the list also
contains water. If instead Water-steam was chosen in the Select System step, the Next
button in that step guides you directly to the Select Thermodynamic Model pane. No
additions of species can be done in the wizard.

608 | CHAPTER 9: THERMODYNAMICS

To add more species to the Dry air and Moist air systems, use the Species Type filter text
field to search among the available species in the COMSOL database or the User-Defined
Species. Species can be searched for by typing the name, CAS number, or the chemical
formula. Select one or more species in the list and click the Add Selected button ( )
to add species to the Selected species table. To remove species from the Selected species
table, use either the Remove Selected button ( ) or the Remove All button ( ),
both located below the table. Click the Next button ( ) to proceed to the next step
in the wizard.

Figure 9-12: Thermodynamic System Wizard: Select Species.

SELECT THERMODYNAMIC MODEL

This last step of the Thermodynamic System Wizard allows you to choose what
thermodynamic model to use. For the system Dry air and Moist air, the Ideal Gas law
is chosen by default. For Water-steam, the model Water (IAPWS) is used. For more
information about this step in the Thermodynamic System Wizard, see Select
Thermodynamic Model for Thermodynamic System.

Click the Finish button ( ) to exit the Thermodynamic System Wizard and add the
corresponding Predefined System under the Thermodynamics node. Note that the
default node label reflects the chosen predefined system.

USING THERMODYNAMIC PROPERTIES | 609

 SETTINGS
Selecting a Predefined System node shows its Settings window with a description of the
package content and the available properties. For information about the content in the
Settings window, see Settings for Thermodynamic System and Predefined System.

MODIFYING A PREDEFINED SYSTEM

Please see Modifying an Existing System for information about how to modify an
existing thermodynamic system.

Exporting and Importing Thermodynamic Systems

EXPORT THERMODYNAMIC SYSTEM

Right-click the thermodynamic system node for the thermodynamic system that you
want to export (Figure 9-8) and select Export Thermodynamic System. Use the Select
File window to store the thermodynamic system.

Note that only the thermodynamic system definition is exported, for example the
underlying species data (from the database), the included phases, and the applied
thermodynamic models. Property values and functions created using the
thermodynamic system are not stored.

IMPORT THERMODYNAMIC SYSTEM

Right-click the Thermodynamics node and select Import Thermodynamic System
(Figure 9-2). Use the Select File window to navigate to a thermodynamic system file
and click Open.

Species Property
A Species Property is used to define and compute a pure species property. The available
properties consist of both parameters and functions. Some examples of available
parameters are molar mass, Lennard Jones diameter, and dipole moment. Some
examples of available functions are density, enthalpy, heat capacity, and viscosity. The
property functions created are either dependent on temperature alone, or both on
temperature and pressure. For all property functions, the first order derivative with
respect to temperature and, when applicable, with respect to pressure are automatically
defined.

610 | CHAPTER 9: THERMODYNAMICS

Right-click the relevant Thermodynamic System node (see Figure 9-8), Predefined
System node, or the relevant External Thermodynamic System node, and select Species
Property ( ) to start the Species Property Wizard.

The Species Property Wizard contains the following steps:

1 Select Properties
2 Select Phase
3 Select Species
4 Species Property Overview

SELECT PROPERTIES
First use the Amount base unit list to define the base unit. Select mol or kg.

Use the filter to search among the available properties. Select one or more properties
in the list and click the Add Selected button ( ) to add them to the Selected properties
list.

Click the Next button ( ) to proceed to the next step, selecting the species.

Figure 9-13: Species Property Wizard; Select Properties.

USING THERMODYNAMIC PROPERTIES | 611

 SELECT PHASE
Use the list to specify the phase for the species property. The available phases
correspond to the ones defined for the thermodynamic system.

Figure 9-14: Species Property Wizard; Select Phase.

Note that for parameters (constants) this step is skipped.

SELECT SPECIES
Select one or more of the species available in the thermodynamic system and use the
Add Selected button ( ) to add them to the Selected species table. One property
function is created for each of the selected species.

Click the Next button ( ) to proceed to the next step in the wizard, which is selecting
the phase for the property.

Figure 9-15: Species Property Wizard; the Select Species step.

SPECIES PROPERTY OVERVIEW

The final step of the wizard presents an overview of the parameters and functions
defined for the corresponding property. Click the Finish button ( ) to exit the wizard
and add the species property to the current thermodynamic system.

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THE SPECIES NODE UNDER A SYSTEM
When creating a species properties, the resulting parameters and functions are
collected under a node with the species name. You can create new functions from an
existing species node under the system. Right-click the species and select Species
Property to start the Species Property Wizard.

Figure 9-16: Create a Species Property from an existing species node.

USING THERMODYNAMIC PROPERTIES | 613

 SETTINGS
Selecting a Species Property node shows the settings for such property.

Figure 9-17: Species Property settings.

Definition:
Shows the definition of a property that is defined as a parameter or a function, for
example the name of the parameter or function.

You can use the Parameter name or Function name fields to specify or change the name
of a parameter or a function. The section also provides information about the property
type and the species it is defined for.

For a parameter, this section also displays the numerical value.

For a function, this sections displays the arguments for the functions and the first order
derivatives with respect to these arguments.

Plot Parameters
Available for property functions in order to plot a selected function for a given set of
argument values.

614 | CHAPTER 9: THERMODYNAMICS

Apply a Lower limit and an Upper limit for each argument, and click the Plot button
( ) to plot the function using the given argument range. You can also click the Create
Plot button ( ) in order to create a plot group, under the Results node.

Properties Window
To see the reference for constant or temperature dependent functions, right-click on
the function and select Properties. This opens the Properties window.

Figure 9-18: Show constant and temperature dependent properties references for species
functions.

The reference for the constant or temperature dependent property is available in the
Comments field in the Node Properties section.

Figure 9-19: Properties window for species function.

USING THERMODYNAMIC PROPERTIES | 615

 Mixture Property
A Mixture Property is used to compute a property function that depends on the
concentration of the species in a thermodynamic system. Some examples of the
available property functions are density, enthalpy, heat capacity, and surface tension.

Apart from the composition, the mixture property functions are also dependent on
temperature and pressure. The first-order derivatives with respect to temperature and
pressure are automatically defined.

Right-click the relevant Thermodynamic System node (see Figure 9-8), Predefined
System node, or the relevant External Thermodynamic System node, and select Mixture
Property to start the Mixture Property Wizard.

The Mixture Property Wizard contains the following steps:

1 Select Properties
2 Select Phase
3 Select Species
4 Mixture Property Overview

SELECT PROPERTIES
The settings in this step corresponds to those for Select Properties in the Species
Property Wizard. Click the Next button ( ) to proceed to the next step.

SELECT PHASE
Use this list to specify the phase, among the ones available in the system, for the
selected mixture property.

Some properties require that the system consists of two phases, for example surface
tension. A two-phase system may consist of a combination of liquid-vapor or
liquid-liquid phases.

SELECT SPECIES
First select the Species composition base unit to be used for function arguments. Select
Mole fraction or Mass fraction.

Select the species to be included in the list. Use the Add All button ( ) to add all
species in the thermodynamic system. It is also possible to select a subset of the
available species. In that case use the Add Selected button ( ) to add species. The
Selected species table is updated as you add species.

616 | CHAPTER 9: THERMODYNAMICS

Click the Next button ( ) to proceed to the next step in the wizard.

MIXTURE PROPERTY OVERVIEW

The final step of the wizard displays an overview of the parameters and functions that
the wizard has added. Click the Finish button ( ) to exit the wizard and add the
properties to the current thermodynamic system.

SETTINGS
Selecting a desired Mixture Property node to display its settings window.

THE MIXTURE NODE UNDER A SYSTEM

When creating mixture properties, the resulting functions are collected under the
Mixture node. You can create new functions from an existing Mixture node. Right-click
the node and select Mixture Property from the context menu to start the Mixture
Property Wizard.

Figure 9-20: Mixture properties can be created by right-clicking a Mixture node under a
thermodynamic system.

Equilibrium Calculation
The Equilibrium Calculation functionality is used to compute the resulting equilibrium
conditions for a mixture of a set of species and phases.

Equilibrium calculations are often used for processes with vapor-liquid equilibrium
(VLE), so-called flash calculations. A typical process that requires flash calculations is
a distillation process, where a multiphase feed stream is separated into a vapor and a
liquid product, and where the concentrations of the species in each phase are required.
Equilibrium calculations involve combining the VLE-equations with material balances

USING THERMODYNAMIC PROPERTIES | 617

 for the chemical species, and in some cases with an energy balance. Flash calculations
are typically used to obtain estimates of:

• Bubble point at given temperature.

• Bubble point at given pressure.
• Dew point at given temperature.
• Dew point at given pressure.
• Equilibrium conditions at given pressure and temperature.
• Equilibrium conditions at given pressure and enthalpy.
• Equilibrium conditions at given pressure and entropy.
• Equilibrium conditions at given internal energy and specific volume.

The last three examples are often considered more difficult, since they require energy
balances and relations for computing enthalpy and entropy. The Liquid & Gas
Properties Module can handle all of the above cases using the equilibrium calculation
functionality. Phase envelopes, bubble point, and dew point can be calculated for any
number of species.

Right-click the relevant Thermodynamic System node (see Figure 9-8), Predefined
System node, or the relevant External Thermodynamic System node, and select
Equilibrium Calculation to start the Equilibrium Calculation Wizard.

The Equilibrium Calculation Wizard consists of the following steps:

1 Select species
2 Equilibrium Specifications
3 Equilibrium Function Overview

The Equilibrium Calculation settings include three types of equilibrium functions.

• The first function type is used to detect whether a phase is present in the system and
includes “exist” in its name.
• The amount function computes the total amount of material in each phase.
• The phase composition functions compute the mass or mole fraction of each species
in each phase, depending on the selected base unit for the equilibrium calculation.

SELECT SPECIES
Select one or more of the species available in the thermodynamic system and use the
Add Selected button ( ) to add them to the Selected species table. Click the Next
button ( ) to proceed to the next step in the wizard.

618 | CHAPTER 9: THERMODYNAMICS

EQUILIBRIUM SPECIFICATIONS
Use the Amount base unit list to use either kg or mol as base unit.

Select two Equilibrium conditions that define the current equilibrium, for example a
given pressure and a temperature. These equilibrium conditions are used as arguments
in the equilibrium functions, in addition to the composition (overall fractions of
species).

The available equilibrium conditions are: Temperature, Pressure, Phase fraction, Energy
(or Internal energy of formation), Enthalpy (or Enthalpy of formation), Specific volume,
Density and Entropy (or Entropy of formation). For chemical reactions, it is
recommended to use Enthalpy of formation, Entropy of formation, or Internal energy of
formation, since they account for heat of reactions.

Figure 9-21: Equilibrium Calculation Wizard; Equilibrium Specifications.

Selecting Phase fraction as one of the equilibrium conditions activates the Solution type
input field. This can be used to indicate the direction of the desired solution, which is
of great use especially near critical points. The options Undefined, Normal, or Retrograde
define different directions for the search of the solution to the equilibrium equations.
Using Normal means that the derivative of the vapor phase fraction with respect to
temperature (at constant pressure and composition) is kept positive and the derivative
of the vapor phase fraction with respect to pressure (at constant temperature and
composition) is kept negative. Using Retrograde means that the opposite sign of the
previous mentioned derivatives are enforced.

USING THERMODYNAMIC PROPERTIES | 619

 For a single species, the critical point is the highest pressure and temperature at which
two phases (liquid and vapor) are distinguishable. However, for some multispecies
systems, the critical point is a point between the dew point and the bubble point. In
this case, the critical point does not represent the maximum pressure or the maximum
temperature of vapor-liquid coexistence. This phenomena is known as retrograde
condensation. This means that under isothermal conditions, when the pressure
decreases, some of the vapor condenses into liquid instead of expanding or vaporizing.
An example of such system is formation of liquid hydrocarbons in a gas reservoir as the
pressure decreases below the dew point pressure. In this case, setting Solution type to
Normal or Retrograde may not be sufficient to distinguish between the two solutions.

Note that the Solution type setting is only available for a built-in thermodynamic
systems. For external thermodynamic systems, the corresponding functionality needs
to be supplied by the thermodynamic software provider. For instance, the
COCO/TEA provider does not support the Normal or Retrograde options. In those
cases, the Solution type should be Undefined.

Click the Next button ( ) to proceed to the next step.

EQUILIBRIUM FUNCTION OVERVIEW

In this step, you can review all the functions including units and arguments. Click the
Finish button ( ) to exit the wizard and add functions at equilibrium state to the
current thermodynamic system.

THE EQUILIBRIUM CALCULATION NODE

When creating an Equilibrium Calculation, the resulting functions are collected under
the Mixture node. You can create new functions from an existing Mixture node.
Right-click it and select Equilibrium Calculation to start the Equilibrium Calculation
Wizard (see Figure 9-20).

SETTINGS
Selecting an Equilibrium Calculation node displays the settings including the property
functions, see Figure 9-22.

620 | CHAPTER 9: THERMODYNAMICS

Plot Parameters:
Can be used to evaluate and plot the equilibrium function for a range of argument
values. First specify which of the included functions to plot. Then apply a Lower limit
and Upper limit for each argument and click the Plot button ( ).

Figure 9-22: Settings window; Equilibrium calculation.

Generate Chemistry
The Chemistry physics interface includes functionality to automatically define and use
mixture properties by interfacing to a Thermodynamic System node. How to manually
set this coupling up is described in Coupling with the Reaction Engineering and the
Chemistry Interfaces.

USING THERMODYNAMIC PROPERTIES | 621

 The Generate Chemistry Wizard can be used to directly create a Chemistry physics
interface from an existing Thermodynamics System node. The resulting Chemistry
interface is automatically populated with the selected species, and is set up to be fully
coupled to the thermodynamics. This means for example that functions for mixture
properties, like the density enthalpy, are automatically defined and used in the
generated Chemistry interface.

Right-click the relevant Thermodynamic System node, Predefined System node, or

External Thermodynamic System node, and select Generate Chemistry to start the
Generate Chemistry Wizard.

The Generate Chemistry Wizard contains the following steps:

1 Select Species
2 Chemistry Settings

SELECT SPECIES
Select the species to be included in the list. Use the Add All button ( ) to add all
species in the thermodynamic system. It is also possible to select a subset of the
available species. In that case use the Add Selected button ( ) to add species. The
Selected species table is updated as you add species.

Click the Next button ( ) to proceed to the next step in the wizard.

CHEMISTRY SETTINGS
The table at the top shows the selected species and their respective chemical formula.
For each species, a corresponding Species feature will be added in the Chemistry
interface. As an option, use the Name in Chemistry columns to specify another name of
the species. By default the chemical formula is used.

Component
Use the Component list to select the model component to which the Chemistry
interface will be added. The already existing components are shown in the top of the
list. A new component can be created by selecting the desired space dimension.

Mass Transfer
The Mass transfer list controls the intended mixture type for the Chemistry interface.
Select Diluted species to model a mixture where the species are assumed diluted in a
high concentration solvent. For this choice, also select Solvent. Optionally, select
Concentrated species to model a mixture where all species are assumed to contribute to

622 | CHAPTER 9: THERMODYNAMICS

the mixture properties. In the resulting Chemistry interface the Type setting in the
Mixture Properties section is defined accordingly.

Phase
Select the Phase of the mixture from the Phase list. Included in the list are the phases
available in the Thermodynamic System from which the Chemistry is generated.

Click the Finish button ( ) to create the desired Chemistry physics interface and exit
the wizard.

Generate Material
Once a thermodynamic system is defined, it can be used to define a multitude of
property functions. The Generate Material option provides a fast route to defining the
material properties most commonly required for fluid flow, heat transfer and mass
transfer. By specifying the composition and the phase of the mixture, a Material node
can automatically be setup. The material node can include properties such as the
density, heat capacity, heat capacity ratio, thermal conductivity and the viscosity. Two
types of property functions can be used. Either functions from the underlying
thermodynamics can be used, or interpolation functions created from these. For
space-dependent models, the interpolation models are more computationally efficient.

Right-click the relevant Thermodynamic System node (or an External Thermodynamic

System node or Predefined System node), and select Generate Material to start the
Generate Material Wizard.

The Generate Material Wizard contains the following steps:

1 Select Phase
2 Select Species
3 Select Properties
4 Define Material

SELECT PHASE
Use this list to specify the phase of the material. Select among the ones available in the
system. This step of the Generate Material Wizard is not available for the Predefined
Systems Dry Air and Moist Air.

Click the Next button ( ) to proceed to the next step in the wizard.

USING THERMODYNAMIC PROPERTIES | 623

 SELECT SPECIES
Select the species to be included in the list. Use the Add All button ( ) to add all
species in the thermodynamic system. It is also possible to select a subset of the
available species. In that case use the Add Selected button ( ) to add species. The
Selected species table is updated as you add species.

Notice that when using Generate Material for the Predefined System Water-steam this
step is not included in the wizard.

Material Composition
Specify the mixture composition in terms of the Mole fractions or Mass fractions of all
species. The fractions should sum to one. This setting is only available for systems with
more than one component, and for materials with more than one selected species.

Click the Next button ( ) to proceed to the next step in the wizard.

SELECT PROPERTIES
Use this step to select the material properties to be included.

For a liquid phase material the following properties are available:

• Density, ()
• Diffusion coefficient at infinite dilution
• Heat capacity (Cp)
• Thermal conductivity (k)
• Viscosity ()

For a gas phase material, the Heat capacity ratio ( = Cp/Cv) is also available.

To add a property to the Selected properties list click the Add Selected button ( ).
To remove properties, use the Remove Selected button ( ) or the Remove All
button ( )

624 | CHAPTER 9: THERMODYNAMICS

When adding the Diffusion coefficient at infinite dilution, also select which of the species
is the solvent. The material will include one diffusion coefficient for each of the
remaining (solute) species.

Figure 9-23: Generate Material Wizard; Select Properties with Diffusion coefficient at
infinite dilution added.

Additional properties
The below additional properties are defined from the selected properties and added to
the output properties of the material.

For a liquid phase material the isobaric coefficient of thermal expansion is defined as:

1 
 iso = – --- ------- (9-1)
 T

For a gas phase material, the speed of sound c, and the isentropic compressibility f are
also defined as:

p 1  (9-2)
c=  ------  f = ------ ------
  p

Click the Next button ( ) to proceed to the next step.

USING THERMODYNAMIC PROPERTIES | 625

 DEFINE MATERIAL

Component
Use the Component list to select where the Material will be added. The already existing
components are shown in the top of the list. A new component can be created by
selecting the desired space dimension. Select Global at the end of the list to add the
material under Global Definitions. A global material can be utilized in any component,
through the use of a Material Link. It can also be used to define phase specific
properties when linked to from a subnode of a Porous Material.

Function Type
The material can be set up to use functions defined under the thermodynamics system,
or interpolation functions defined from these. The interpolation functions are
significantly faster to evaluate, especially for space dependent models, but requires that
the temperature range and the pressure range is specified.

Select Thermodynamics to base the material properties on functions in the current

thermodynamic system. The required functions are created, if not already present, and
added to the system. When evaluating material properties, the underlying
thermodynamics functions are called.

Select Interpolation to generate interpolation functions for the material properties. In

this case the required functions are first created and added to the system. Next, the
functions are evaluated in a number of sampling points over a given range, for both
temperature and pressure. The result of the evaluation is stored and used to define
interpolation functions for all material properties.

For the Interpolation points, select Same for all functions to use the same number of
evaluation points for all function. By selecting Individual, the number of evaluation
points can be given per function. The latter can for example be used to increase the
number of points for a function that is known to vary faster than the rest of the
functions.

Select one of the preset levels for the Maximum number of interpolation points. This is
used to provide a maximum size of the underlying data for the interpolation functions.
If the total number of evaluation points for any function, varying temperature and
pressure, is exceeded, a warning is shown.

Define the temperature range for the temperature and pressure by providing the Low
and High end values. To neglect the variation in either temperature or pressure, give
the same value for the low and high end value. This can for example be used when the
pressure variation is known to be negligible. For each range, also define the number of

626 | CHAPTER 9: THERMODYNAMICS

evaluation points in the Number of points field. The underlying functions are evaluated
at uniformly distributed positions across the temperature and pressure range.

When Individual has been selected for the Interpolation points, the Ranges and
interpolation points can be specified per function to be created.

Click the Finish button ( ) to create the specified Material and exit the wizard.

Coupling with the Reaction Engineering and the Chemistry

Interfaces
Using the Reaction Engineering or Chemistry interfaces, all species property parameters
and property functions required by these interfaces can be created automatically by
coupling to an existing Thermodynamic System, Predefined System, or External
Thermodynamic System under Thermodynamics. Examples of species properties that can
be created automatically are molar mass, heat capacity, enthalpy, and entropy for each
species. Parameters and functions for these properties are created by the
thermodynamic system. The Reaction Engineering and Chemistry interfaces can also be
used to define transport properties for the resulting mixture (all species in the
interface). When coupled, the following mixture properties can be automatically
created: heat capacity, density, thermal conductivity, and dynamic viscosity.

This Reaction Engineering interface and the Chemistry interface are only
available in a limited set of add-on products. See
https://www.comsol.com/products/specifications/ for more details on
availability.

Note that using a thermodynamic system significantly increases the modeling

capabilities in the Reaction Engineering and Chemistry interfaces. All ideal and nonideal
thermodynamic models, for gases and liquids, are directly available and also
automatically updated by editing the settings for the thermodynamic system in use.
The Chemistry interface can furthermore be used to make the mixture properties
readily available in space-dependent models for modeling of mass transport, heat
transfer, or fluid flow.

REACTION ENGINEERING

Mixture Properties
You can couple a Reaction Engineering interface with an existing thermodynamic
system in the Reaction Engineering interface’s settings window.

USING THERMODYNAMIC PROPERTIES | 627

 You need to have at least one species defined in the Reaction Engineering interface in
order to couple it to a thermodynamic system. You can make this coupling in the
Settings window for the Reaction Engineering interface by selecting the Thermodynamics
check box in the Mixture Properties section.

Select a thermodynamic system from the Thermodynamic system list. Use the Phase list
to select the phase to be used in the Reaction Engineering interface.

Figure 9-24: Coupling Reaction Engineering Interface with Thermodynamics.

Species Matching
The Species Matching section is activated when the Thermodynamics check box is
selected in the Mixture Properties section; see above. The species in the Reaction
Engineering interface can be matched to a species in the thermodynamic system. This
step ensures that the arguments in the thermodynamic system functions are correctly
defined.

Use the lists in the From Thermodynamics column to match each species in the interface
to a species in the coupled thermodynamic system.

For each species matched, the required property parameters and functions are added
under to the corresponding thermodynamic system.

When all species are matched, the interface is considered fully coupled and functions
representing mixture properties, such as density, are also added automatically under
the corresponding thermodynamic system.

Figure 9-25: Matching the species in Reaction Engineering to those in the corresponding
thermodynamic system.

628 | CHAPTER 9: THERMODYNAMICS

Calculate Transport Properties
When the interface is fully coupled to a thermodynamic system, property functions for
the mixture transport properties are created automatically when the Calculate mixture
properties check box is selected. The properties calculated by the thermodynamic
system display Thermodynamics in the corresponding list; see below.

Figure 9-26: Select the Calculate mixture properties check box when coupled to a
thermodynamic system.

CHEMISTRY

Mixture Properties
You can couple a Chemistry interface with an existing thermodynamic system in the
Chemistry interface’s settings window. You can make this coupling in the Settings
window for the Chemistry interface by selecting the Thermodynamics check box in the
Mixture Properties section. You need to have at least one species defined in the
Chemistry interface in order to couple it to a thermodynamic system.

Select a thermodynamic system from the Thermodynamic system list. Use the Phase list
to select the phase to be used in the Chemistry interface.

Species Matching
The Species Matching section is activated when the Thermodynamics check box is
selected in the Mixture Properties section. Here you can match the variables for the
concentrations, and by this calculate mixture properties (transport and thermodynamic
properties). For information on how to specify the dependent variables to be used, see
Species Matching in The Chemistry Interface documentation.

You can match the species in the Chemistry interface with those in the corresponding
thermodynamic system in the Species matching section’s table. Use the lists in the
column with the title From Thermodynamics to match each species in the Chemistry
interface to a species in the corresponding thermodynamic system. This ensures that
the composition function arguments in the thermodynamic system are correctly
defined.

USING THERMODYNAMIC PROPERTIES | 629

 For each species matched, the species property parameters and functions required by
the Chemistry interface are automatically created and added under the corresponding
thermodynamic system.

When all species are matched, the interface is fully coupled to Thermodynamics and
functions representing mixture properties, such as the density, are added automatically
under the thermodynamic system that the interface is coupled to.

Figure 9-27: Matching concentration variables in a Chemistry interface, as well as species

in a coupled Thermodynamic System.

Calculate Transport Properties

When the interface is fully coupled to a thermodynamic system, property functions for
the mixture transport properties are created automatically when the Calculate mixture
properties check box is selected. The properties calculated by the thermodynamic
system display Thermodynamics in the corresponding list; see Figure 9-26.

MIXTURE PROPERTY DEFINITIONS WHEN COUPLING TO

THERMODYNAMICS
When all species in a physics interface are matched to the corresponding species in a
thermodynamic system, the mixture properties are calculated based on the
composition of the mixture. For example, consider Zmix(T, P, n1,..., nm), which
denotes a generic extensive mixture property for a mixture of m number of species.
The property function’s arguments are temperature T, pressure P, and the number of
moles, n, for each species.

When the system is fully matched, the mixture property Zmix is defined as:

m
Z mix =  ni Zi (9-3)
i=1

630 | CHAPTER 9: THERMODYNAMICS

where Z i is the partial molar of species i:

Z mix  T P n 1 n 2  n m 
Z i =  ----------------------------------------------------------------------- (9-4)
 ni  T P n
ji

The definition of partial molar properties can be rewritten using mole fraction
derivatives as:

Z i  T P n 1  n m  = Z i  T P x 1  x m  = (9-5)

 Z mix  T P x 1  x m 
Z  T P x 1  x m  +  ------------------------------------------------------------
 mix  xi  T P x
 ij

m Z mix  T P x 1  x m  
 x  ----------------------------------------------------------- 
–   i xi
-
 T P x  
i=1
ij


When the system is partially coupled, which means that some but not all species have
been coupled, the mixture property is instead calculated assuming ideal mixing:

m
Z mix =  ni Zi  T P  (9-6)
i=1

using the pure species properties Zi  ZmixTPxi =10…0.

Evaluating a Property Function in a Physics Interface

The functions set up using a thermodynamic system in Thermodynamics can be used
directly in any physics interfaces in COMSOL Multiphysics, in the same way as for
standard functions. Simply type in the function name with the proper arguments in the
appropriate field of the model to use the function. Figure 9-28 shows an example of
this from the Reaction Engineering interface. In this example, the Species
Thermodynamic Expressions section gets input for the molar entropy, the enthalpy and
the heat capacity of toluene. These functions, generated using Species Property for a

USING THERMODYNAMIC PROPERTIES | 631

 thermodynamic system containing toluene, have been entered in the corresponding
input fields using the appropriate arguments.

Figure 9-28: The enthalpy and heat capacity of toluene are evaluated using property
calculations through a thermodynamics system. In this case, the functions are temperature
and pressure dependent properties for a pure component.

User-Defined Species
Use this feature to specify the properties of a new species not available in the included
COMSOL database. This feature can also be used to edit a database species, by using
an existing species as a template, to create a new one. A User-Defined Species can be
included in a Thermodynamic System feature, or Predefined System feature, together
with predefined database species and other user-defined species.

The data needed for a user-defined species includes both material properties, such as
the molar mass and the vapor pressure, and properties for specific thermodynamic
models or transport models (see Thermodynamic Models and Theory). For instance,
in order to use the UNIFAC thermodynamic model, you need to define UNIFAC
groups for the new species.

Note that the thermodynamics calculator includes measures to handle missing species
properties, sometimes by applying approximations. For instance, if the Wilson volume
is not available, the liquid volume at normal boiling point is used instead. If data for
this is also missing, it is estimated from the saturated liquid density correlation.

When creating a user-defined species it is recommended to add the following common

material properties:

• Molecular mass
• Critical properties
• Acentric factor

632 | CHAPTER 9: THERMODYNAMICS

• Absolute entropy
• Standard enthalpy of formation
• Ideal gas heat capacity
• Vapor pressure
• Heat of vaporization
• Saturated liquid density
• Transport properties

EXAMPLE MODEL
For an example of using a User-Defined Species see this application example:

Dissociation in a Tubular Reactor: Application Library path

Chemical_Reaction_Engineering_Module/Thermodynamics/dissociation

THE USER-DEFINED SPECIES WIZARD

To create a User-Defined Species, start the User-Defined Species Wizard in one of the
following ways:

• Right-click the Global Definitions node, select Thermodynamics and choose

User-Defined Species.
• If the model already includes the Thermodynamics node, right-click it and choose
User-Defined Species.
• Using the Reaction Engineering interface, or Chemistry interface, choose
User-Defined Species from the Thermodynamics section of the Reaction Engineering, or
Chemistry toolbar.

The User-Defined Species Wizard contains the following steps:

1 Enter Name and Formula

2 Enter Parameters
3 Define Properties

USING THERMODYNAMIC PROPERTIES | 633

 ENTER NAME AND FORMULA
Enter the Name, CAS number, and the Chemical formula for the new species.

Figure 9-29: User-Defined Species Wizard; Enter Name and Formula.

If you want to edit a species in the COMSOL database, select the Use species from
database as template check box. Then locate the species to edit in the list. The filter
text field can be used to search among the available species.

Figure 9-30: User-Defined Species Wizard; edit an available species by selecting

Use species from database as template.

Click the Next button ( ) to proceed to the next step.

ENTER PARAMETERS
Define the necessary parameter for the new species.

634 | CHAPTER 9: THERMODYNAMICS

Constants
Use this table to define material constants such as molar mass, critical temperature, and
standard enthalpy of formation.

Figure 9-31: User-Defined Species Wizard; Enter material constants.

Structure information
If you want to use the UNIFAC model, specify the structure formula, the UNIFAC
groups and their number occurrences.

Figure 9-32: User-Defined Species Wizard; Specify the structure information in the Enter
Parameters step.

USING THERMODYNAMIC PROPERTIES | 635

 Model parameters
Specify the parameters for the thermodynamic models and transport models in use.

Figure 9-33: User-Defined Species Wizard; Specify model parameters.

Click the Next button ( ) to proceed to the next step.

DEFINE PROPERTIES
The last step in the wizard is to add temperature dependent properties for the new
species. All temperature dependent properties are defined using cubic polynomials on
the form

2 3
f  T  = a0 + a1 T + a2 T + a3 T (9-7)

Each property can consist of an arbitrary number of temperature intervals, each using
the above form. Click the Add button ( ) under the table for a specific property to
add an interval.

The following temperature dependent properties are necessary in order to compute

the basic set of mixture properties when including the User-Defined Species in a
thermodynamic system:

• Ideal gas heat capacity

• Liquid density
• Vapor pressure
• Heat of vaporization

Note that some thermodynamic properties, such as the enthalpy and entropy, of a
species or mixture, are estimated from the ideal gas heat capacity and depends on the
thermodynamic model applied for the system (see Thermodynamic Properties
Definitions).

636 | CHAPTER 9: THERMODYNAMICS

Click the Finish button ( ) in the top of the Settings window to finalize the species
and add it to the User-Defined Species node under Thermodynamics.

Figure 9-34: User-Defined Species Wizard; specify temperature-dependent properties.

SETTINGS
Selecting a species node under User-Defined Species shows the Settings window
including the definitions of all species properties. Properties are categorized into
sections as seen in Figure 9-35 below. All properties can be edited by expanding the
corresponding section.

When a species properties has been changed, any Thermodynamic System

that includes the species needs to be updated for the changes to take effect
(see Update From Species).

USING THERMODYNAMIC PROPERTIES | 637

 Figure 9-35: The Settings window for a User-Defined Species.

References
1. www.colan.org

2. Cape Open to Cape Open Simulation Environment,

www.cocosimulator.org/index_download.html

638 | CHAPTER 9: THERMODYNAMICS

Thermodynamic Models and Theory
In this section:

• Introduction
• Thermodynamic Models
• Selecting the Right Thermodynamic Model
• Species Property References
• Thermodynamic Properties Definitions
• Standard Enthalpy of Formation and Absolute Entropy Terms
• Reference State
• Transport Properties
• Surface Tension
• References

Introduction
In this chapter, we review the theory behind the thermodynamic properties database
and its functions. The thermodynamic models in the database are available for single
phase, gas or liquid, and phase equilibrium systems for two or more phases such as
vapor-liquid equilibrium (VLE), vapor-liquid-liquid equilibrium (VLLE) and
liquid-liquid equilibrium (LLE).

Thermodynamic Models
In the following sections, the available thermodynamic models are described:

• Equation of State Models

• Liquid Phase Models

EQUATION OF STATE MODELS

An equation of state (EOS) model is an algebraic relation between the absolute
pressure (P), the molar volume (V), and the absolute temperature (T). An equation of
state that is at least cubic in volume and in the form of

PV
Z  -------- = f v  V T  (9-8)
RT

THERMODYNAMIC MODELS AND THEORY | 639

 where Z is the compressibility factor and R the universal gas constant, can be used to
describe both gases and liquids. The cubic equations of state are widely used to
describe the gaseous and liquid volumetric behavior of pure fluids and also all other
properties with extensions to mixtures. A comprehensive comparisons of different
cubic EOS can be found in Ref. 4 and Ref. 5.

The equation of state models available in the thermodynamic properties database are:

• Ideal Gas Law

• Peng-Robinson
• Peng-Robinson (Twu)
• Soave-Redlich-Kwong
• Soave-Redlich-Kwong (Graboski-Daubert)
• Water (IAPWS)

Ideal Gas Law

The ideal gas law equation of state is

RT
P = -------- (9-9)
V

As the name suggests, the ideal gas law is only applicable to gases. In fact, its use is
limited to gases at low to moderate pressures.

Peng-Robinson
The classical Peng-Robinson (PR) equation of state Ref. 7 is given by

RT a
P = ------------- – ------------------------------------
- (9-10)
V – b V 2 + 2bV – b 2

where for species i

2 2
R Tc
a i =  A -------------- (9-11)
Pc

RT c
b i =  B ----------- (9-12)
Pc

1 1
 A = --- + ---  B  4 + 10 B  (9-13)
3 3

640 | CHAPTER 9: THERMODYNAMICS

  B =   – ----------------- – 0.03125
63
(9-14)
 1024 

The alpha function, i, is given by

2
 i =  1 +  0.37464 +1.54226 i – 0.26992 i2   1 – T r i   (9-15)

For mixtures

  xi xj  1 – kPR,i,j 
a =  a  i  a  j (9-16)
i j

 xi bi
b = (9-17)
i

The binary interaction parameters (BIPs), kPR, are symmetric with zeros in the
diagonal:

k PR = k PR,i,j (9-18)

k PR,i,j = 0 (9-19)

When binary interaction parameters are missing in the database for a set of species, the
value is set to zero (a warning node is created). The values for critical temperature, Tc,
critical pressure, Pc, and acentric factor, i must be specified for all species.

Peng-Robinson (Twu)
For the Twu modificationRef. 8 of the Peng-Robinson model, the alpha function, i,
is replaced by

 Ni  Mi – 1   NM
i = T + R exp  L i  1 – T r ii i   (9-20)

The binary interaction parameters kPR, are used for the Twu modification. Acentric
factor, i, is not used in this model but critical temperature and critical pressure must
be specified for all species. The species specific fit parameters Li, Mi, Ni can be
determined by fitting the pure species phase equilibrium to the vapor pressure curve.

Soave-Redlich-Kwong
The classical Soave-Redlich-Kwong equation of state Ref. 9 is given by

RT a
P = ------------- – ----------------------- (9-21)
V – b V V + b

THERMODYNAMIC MODELS AND THEORY | 641

 with

1
 = -------- (9-22)
T

and for the pure species i,

2 2.5
R Tc
a i =  A ------------------ (9-23)
Pc

RT c
b i =  B ----------- (9-24)
Pc

1 1
 A = --- + ---  B  3 + 3 B  (9-25)
3 3

1 2
--- ---
1 3 3 1
B = ------ 2 27 – --- (9-26)
27 3

For mixtures

  xi xj  1 – kSRK,i,j 
a = ai aj (9-27)
i j

 xi bi
b = (9-28)
i

The binary interaction parameters, kSRK, are symmetric with zero in the diagonal:

k SRK ,i,j = k SRK ,j,i (9-29)

k SRK ,i,j = 0 (9-30)

If a value is missing for kSRK,i,j in the database, it is set to zero (a warning node is
created). The Values for critical temperature, Tc, critical pressure, Pc, and acentric
factor, i, must be specified for all species. The Soave-Redlich-Kwong equation of state
is a version of Equation 9-21 modified by Soave Ref. 10, where for pure species i, the
alpha function is modified to

2
 i =  1 +  0.480 +1.574 i – 0.176 i2   1 – T r i   (9-31)

642 | CHAPTER 9: THERMODYNAMICS

Soave-Redlich-Kwong (Graboski-Daubert)
The Graboski and Daubert Ref. 11 modification of the Soave-Redlich-Kwong
equation of state replaces alpha function by

2
 i =  1 +  0.48508 +1.55174 i – 0.1561 i2   1 – T r i   (9-32)

except for H2, where it is replaced by

 H 2 = 1.202 exp  – 0.30228T r H 2  (9-33)

Water (IAPWS)
The International Association for the Properties of Water and Steam (IAPWS)
provides a set of correlations to compute properties of water in different states. The
correlations available in COMSOL correspond to the version named Industrial
Formulation 1997 (IF-97) Ref. 12 - Ref. 14. The correlations are valid in the
following ranges:

273.15 K  T  1073.15 K p  100 MPa (9-34)

1073.15 K  T  2273.15 K p  50 MPa (9-35)

The following water and steam properties, available by creating a Species Property, are
computed using the IAPWS correlations: density, volume, enthalpy, internal energy,
Helmholtz energy, heat capacity at constant pressure, and heat capacity at constant
volume. The amounts present in the vapor and liquid phase can be computed using an
Equilibrium Calculation.

Other parameters and thermodynamic properties available for the system are provided
from COMSOL database.

LIQUID PHASE MODELS

Activity coefficient models

Activity coefficient models are used to describe liquid mixtures at low to moderate
pressure and temperature but where equations of state are inadequate. When using
activity coefficient models, the partial fugacity for species i in the liquid phase is defined
as

f̂ i l = x i  i  i sat P i sat F i (9-36)

which yields

THERMODYNAMIC MODELS AND THEORY | 643

 P i sat
̂ i l =  i  i sat ------------- F i (9-37)
P

where the activity coefficient, i, describes the nonideal liquid phase and ̂ i sat P i sat
is the fugacity at the vapor-liquid phase boundary at equilibrium for the pure species
i. The Poynting correction, Fi, describes the pure species fugacity deviation from the
boiling curve and can be expressed as

 P V i l 
F i = exp 
 P i sat
--------- dp
RT 
(9-38)

For an incompressible liquid, an approximation of the Poynting correction can be

done according to

V i l
F i  exp  ---------  P – P i sat  (9-39)
RT

The Poynting correction can often be ignored for moderate pressure. Hence,
Equation 9-37 can be expressed as

P i sat
̂ i l =  i  i sat --------------- (9-40)
P

If the vapor phase is considered ideal, then  i sat = 1 and the above equation reduces
to

P i sat
̂ i l =  i --------------- (9-41)
P

This reduction can be selected explicitly in case the vapor phase is not ideal.

The logarithmic transformation of Equation 9-37 is:

ln ̂ i l = ln  i + ln  i sat + ln P i sat – ln P + ln F i (9-42)

Ideal Solution
For an ideal solution the activity coefficient is equal to one, which gives:

ln  i = 0 (9-43)

Regular Solution
The Scatchard-Hilderbrand equation Ref. 16 for a nonpolar mixture is

644 | CHAPTER 9: THERMODYNAMICS

 2
V i   i –  av 
ln  i = --------------------------------- (9-44)
RT

where Vi is species molar volume and i is species solubility parameter, and av is

  xi Vi i  (9-45)
 av = ----------------------------
i


 xi Vi 
i

The volume parameter, Vi, is set equal the liquid volume, Vi,l,b at normal boiling point
which must be specified for all species. The solubility parameter, i must be specified
for all species and can be estimated from the normal heat of vaporization, Hvap,iand
the liquid volume at normal boiling point as below:

H vap i
 i  --------------------
- (9-46)
V i l b

Extended Regular Solution

The extended Scatchard-Hildebrand equation adds the Flory and Huggins correction
to the regular solution model Ref. 18:

2
V i   i –  av 
ln  i = --------------------------------- + ln   i  + 1 –  i (9-47)
RT

where

Vi
 i = ----------------------- (9-48)
  xi Vi 
i

Wilson
Wilson Ref. 19 derived his activity coefficient model from a consideration of
probabilities of neighboring molecules in a liquid

 
 x    (9-49)
 -----------------------
j j i 
ln  i = 1 –  
- – ln 
   xj i j
j
 
 x k  j k

j
k

THERMODYNAMIC MODELS AND THEORY | 645

 V w j  i j
 i j = ----------- exp  – -------- (9-50)
V w i  T

where the Wilson volume parameter, Vw,i, is a species-specific parameter describing

volume. If the volume parameter is not available, the liquid volume at normal boiling
point is used. The Wilson binary interaction parameters i,j are specified in terms of
absolute temperature. The binary interaction parameter matrix is nonsymmetric and
with zeros in its diagonal. All off-diagonal values must be specified

 i i = 0 (9-51)

 i i = 1 (9-52)

NRTL
Renon and Prausnitz (Ref. 20) formulated a three parameter activity coefficient model
that is able to describe liquid-liquid equilibrium; the nonrandom two-liquid (NRTL)
model:

  
 xj j i Gj i 
 x j G j i 
  x k  k j G k j 
 (9-53)
ln  i = ------------------------------   -------------------------   i j – ----------------------------------
j -+ k

 x G  
 x j G j i j   k k j   x G
k k j  
j  k  k 

A i j
 i j = --------- (9-54)
T

G i j = exp  –  i j  i j  (9-55)

The three parameters are Ai,j, Aj,i, and i,j. A more general form is implemented here:

A i j
 i j = --------- + B i j (9-56)
T

G i j = exp   i j –  i j  i j  (9-57)

The binary interaction parameters, Ai,j, are specified in terms of absolute temperature.
The diagonal values are zero and the matrix is nonsymmetric. All off-diagonal values
must be specified.

The binary interaction parameters, Bi,j, have values of zero on the diagonal and the
matrix is nonsymmetric. For each pair of species at least Ai,j or Bi,j should be specified.

646 | CHAPTER 9: THERMODYNAMICS

The randomness parameters, i,j, have values of zero on the diagonal and the matrix
is symmetric. All off-diagonal values must be specified. Alternatively one can set the
more generic form directly specifying parameter i,j for which diagonal values are zero
and the matrix is nonsymmetric. For each pair of species at least i,j or i,j should be
specified.

If any value for these parameters is missing in the database, it is set to zero (warning
node is created).

A i i = 0 (9-58)

B i i = 0 (9-59)

 i i = 0 (9-60)

 j i =  i j (9-61)

 i i = 0 (9-62)

G i i = 1 (9-63)

 i i = 0 (9-64)

UNIQUAC
Abrams and Prausnitz followed up with another two-liquid model known as Universal
Quasi Chemical equation (UNIQUAC) Ref. 21 which is formulated in terms of two
activity coefficients:

ln  i = ln  i comb + ln  i res (9-65)

The first term is the combinatorial part contributes to the Gibbs free energy
originating from size and shape effects as

i i
ln  i comb = 1 –  i + ln  i – --- q i  1 + ---- + ln  ---- 
z
(9-66)
2 i i

and the second term is the residual part from chemical interactions between the
molecules,

THERMODYNAMIC MODELS AND THEORY | 647

    

  j

 x j q j  j i
 x j q j  j i 

ln  i res = q i  1 – ln  -------------------------
 
- –
 -
-------------------------- (9-67)
 x j q j  x j q j  k j



 j 
j  
k
where

ri
 i = ----------------- (9-68)
 xj rj
j

qi
 i = ----------------- (9-69)
 xj qj
j

–  E i j
 i j = exp  ----------------- (9-70)
T

The coordination number is taken equal to z = 10. The binary interaction energy
parameters, Ei,j, are specified in terms of absolute temperature (K). The diagonal
values are zero and the matrix is nonsymmetric. All off-diagonal values must be
specified.

E i i = 0 (9-71)

 i i = 1 (9-72)

The volume parameters, ri and surface area parameters, qi are model-specific

parameters for each species. If the parameters are not specified then they can be derived
from the van der Waals volume, VVDW,i, and area, AVDW,i, respectively

V VDW i
r i = -----------------------------------
–3
- (9-73)
0.01517 10

A VDW i
q i = -------------------5- (9-74)
2.5 10

For all species ri or VVDW,i and qi or AVDW,i must be specified.

UNIFAC
The UNIQUAC Functional-group Activity Coefficients (UNIFAC; see Ref. 22) uses
the same equations as UNIQUAC but the parameters are constructed from group

648 | CHAPTER 9: THERMODYNAMICS

contributions. The model can be used if UNIQUAC parameters are not available for
all species. The activity coefficients are calculated from Equation 9-65. The
combinatorial part follows from equation Equation 9-66, where

ri =   k i r k (9-75)
k

qi =   k i q k (9-76)
k

where rk and qk are the values for group k in species i, andk,i is the number of
occurrences of group k in molecule. The residual term in Equation 9-65 is calculated
from a summation over functional groups:

ln  i res =  k i  ln k res – ln i k res  (9-77)

k

The values for ln(k,res) are calculated from the mixture containing all species at a
specified composition x. The values for ln(i,k,res) are calculated for a mixture of group
k considering only pure species i. Both are defined, for functional group k, by
   

  l

 x l q l  l k
 x l q l  k l 

ln  k res = q k  1 – ln  --------------------------
 
- –
 ----------------------------- (9-78)
x l q l 
 x l q l  m l



 l 
j  
m
where xl and xm are the compositions of functional group l and m in the mixture

 x i  m i
i
x m = ----------------------------------- (9-79)
 
 
 x i  k i
 
i k
For the calculation of a pure species’ i residual activity we get:

 m i
x m = ----------------- (9-80)
 k i
k
The volume parameters rk and surface area parameters qk are model-specific
parameters for each group. The binary interaction between groups k and m is

THERMODYNAMIC MODELS AND THEORY | 649

 A k m
 k m = exp  – ------------- (9-81)
 T 

The binary interaction parameters, Ak,m, are specified in terms of absolute

temperature. The diagonal values are zero, the matrix is nonsymmetric. All
off-diagonal values must be specified.

The default group and interaction parameters are those published by the UNIFAC
consortium (Ref. 23 through Ref. 28), with added groups from Balslev and Abildskov
(Ref. 29) but can be modified per package or database. The groups must be specified
for all species. Note that the interaction parameter matrix is sparse, and a package can
only be used if all interaction parameters for all used groups are specified.

Chao Seader (Grayson-Streed)

The Chao-Seader model Ref. 15 correlates liquid phase partial coefficients for pure
species, for use of hydrogen and hydrocarbon mixtures at elevated pressure and
temperatures. It is expressed by

ln  i l = ln  i + ln  i l 0 (9-82)

The activity is based on the Scatchard-Hildebrand equation Ref. 16 and presented in

Equation 9-44 to Equation 9-46. Chao-Seader specific values for liquid volume, Vi
and solubility parameter, i are used.

If Vi is unspecified, it can be estimated by

a molar volume at normal boiling point

b van der Waals volume
c from the Rackett model, Equation 9-79, at normal boiling point temperature.
If the Chao-Seader specific solubility parameter, i, is not specified, the generic
solubility parameter is used.

The fugacity coefficient for pure species i is correlated as

log  i l 0 = log  i l 1 +  i log  i l 2 (9-83)

A i 1
log  i l 1 = A i 0 + ---------- + A i 2 T r i + A i 3 T r2 i + A i 4 T r3 i (9-84)
T r i

+  A i 7 T r2 i + A i 6 T r i + A i 5 P r i +  A i 9 T r i + A i 8 Pr2 i – log P r i

650 | CHAPTER 9: THERMODYNAMICS

 A i 12
log  i l 2 = A i 10 + ------------- + A i 11 T r i + A i 13 T r3 i + A i 14  P r i – 0.6  (9-85)
T r i

A Chao-Seader specific acentric factor i is used. If it is unknown, it can be set equal

to the generic acentric factor. The parameter values are taken from the later publication
of Grayson and Streed Ref. 17 and given in Table 9-1.
TABLE 9-1: CHAO-SEADER GRAYSON-STREED FUGACITY COEFFICIENT PARAMETERS.

H2 CH4 OTHER ALL

Ai,0 1.50709 1.36822 2.05135 Ai,10 -4.23893

Ai,1 2.74283 -1.54831 -2.10899 Ai,11 8.65808
Ai,2 -0.02110 Ai,12 -1.22060
Ai,3 0.00011 0.02889 -0.19396 Ai,13 -3.15224
Ai,4 -0.01076 0.02282 Ai,14 -0.02500
Ai,5 0.008585 0.10486 0.08852
Ai,6 -0.02529
Ai,7 -0.00872
Ai,8 -0.00353
Ai,9 0.00203

The corresponding vapor phase model is Redlich-Kwong equation of state. The

Chao-Seader (Grayson-Streed) model is valid when

- 255 K < T < 533 K

- P < 6.89 MPa
- Pr < 0.8
- 0.5 < Tr,i < 1.3, for all hydrocarbons except CH4
- xCH4 < 0.3
- For system that includes CH4 or H2S:

 xi Tr i  0.93
i

The enthalpy, entropy and Gibbs free energy can be calculated from Equation 9-108
to Equation 9-117.

THERMODYNAMIC MODELS AND THEORY | 651

 LIQUID VOLUME MODELS
When an activity coefficient model or the Chao-Seader (Grayson-Streed) model is
used, a liquid volume model must be explicitly selected. It is also possible to assign a
liquid volume model when an equation of state is used.

For liquids the density is defined as the reciprocal of the liquid volume:

1
 l = ------ (9-86)
Vl

Equation of State
When an equation of state is selected as the thermodynamic model, the liquid volume
is calculated using the equation of state model. In the other cases, when the
thermodynamic model is not an equation of state, an equation of state can be explicitly
selected to calculate the liquid volume.

Note, when defining the equation of state for vapor and liquid systems, both phases
must use the same equation of state.

Ideal Mixture
For an ideal mixture the liquid volume is computed from the pure species densities:

xi
V l m =  --------
 i l
(9-87)
i

The pure species densities are evaluated from the built-in database.

COSTALD
Hankinson and Thomson Ref. 30 presented the Corresponding States Liquid Density
(COSTALD) equation as

V -
------------ = V r ref  1 – V r   (9-88)
V mix

V r ref = 1 + a  1 – T r  1 / 3 + b  1 – T r  2 / 3 + c  1 – T r  + d  1 – T r  4 / 3 (9-89)

e + fT r + gT r2 + hT r3
V r  = ---------------------------------------------------- (9-90)
T r – 1.00001

1   
V mix = --- 
4  xi Vi + 3   xi Vi2 / 3   xi Vi1 / 3  (9-91)
i i i

652 | CHAPTER 9: THERMODYNAMICS

  
 
 x i T c i V i

i
T c = ------------------------------------------ (9-92)
V mix

 -----
T
 T- T  Tc
Tr =  c (9-93)
1 T  Tc


 =  xi i (9-94)
i

where the volume, Vi and acentric factor, ifor species i are model specific parameters.
If the COSTALD volume parameter is unspecified, it is estimated from the van der
Waals volume when VVDW,i> 0.3-3 m3/mol

2
V i = 5.385 V VDW i – 5.1022VVDW 3
+ 79.524VVDW (9-95)
i i
4 5 6
– 99.316VVDW i + 100.88VVDW i – 1152.7VVDW i

otherwise it can be set equal to the critical volume as

V i = V c i (9-96)

If the COSTALD acentric factor, i is not specified then it can be set equal to the
generic acentric factor for species i. Critical temperature, Tc,i must be specified for all
species.

The correlation parameter values are:

TABLE 9-2: REDUCED VOLUME CORRELATION PARAMETERS IN COSTALD.

a -1.52816 e -0.296123
b 1.43907 f 0.386914
c -0.81446 g -0.0427258
d 0.190454 h -0.0480645

Rackett
The Rackett equation Ref. 31 computes the liquid density at the saturation point, and
can be used to describe liquid density at any pressure using the assumption that the
liquid is incompressible. The equation and its condition can be expressed as:

THERMODYNAMIC MODELS AND THEORY | 653

  x i T c i     1 +  1 – Tr 2  7   
2

Vl =  R
  - 
---------------------------
 MW  i P c i   Z r i


  xi  MW i (9-97)
i i i

 xi Tc i
Tc = (9-98)
i

 -----
T
 T- T  Tc
Tr =  c (9-99)
1 T  Tc


Critical temperatures, Tc,i, critical pressures, Pc,i, and molecular weights, Mi, must be
specified for all species. The model parameter, Zr,i, must be specified for all species. If
the value is not available it can be set to the critical compressibility factor:

Z r i = Z c i (9-100)

Selecting the Right Thermodynamic Model

There are methods to choose the appropriate thermodynamic models; see Ref. 78.
This choice depends on the nature of the property, composition of the mixture,
operational pressure and temperature, and availability of model’s parameters for the

654 | CHAPTER 9: THERMODYNAMICS

simulation; see Ref. 79. Below is a decision tree that can be used as a guide for
choosing the thermodynamic model:

Figure 9-36: Decision tree to select thermodynamics model.

It is possible to manually modify the species properties, such as parameters and

temperature-dependent functions, in the database file. In the same manner, you can
manually add new species that do not exist in the database. To do this, right-click a
system node under Thermodynamics and select Export thermodynamic system. Save the
thermodynamic system as an xml file.

All the parameters and temperature-dependent properties are saved inside a

<Compound CompID="name"></Compound> block. For example, to edit the acentric
factor of methane from 0.01141 to 0.2 perform the following steps

• Open the saved xml file for the thermodynamic system

• Find the compound methane which starts with the line:
<Compound CompID="methane">

THERMODYNAMIC MODELS AND THEORY | 655

 • Find the line with the acentric factor and change it to
<AcentricFactor >0.2</AcentricFactor>.

To use the system with the updated species, right-click the Thermodynamics node and
select Import System.

For temperature-dependent functions, for example for the (saturated) liquid density,
the database input is of the form:

<Density>
<Phase>Liquid</Phase>
<Coefficients>Tlb;a0;a1;a2;a3;Tub</Coefficients>
<Data>Tlb;f(Tlb);Tub;f(Tub)</Data>
<Comment></Comment>
</Density>

Here Tlb and Tub defines the lower and upper bound for a temperature range, and a1
to a4 are the corresponding coefficients for a cubic polynomial as f(T) = a0 + a1T+
a2T2+ a3T3 fitted for that range. Multiple sequential ranges can be added by
appending temperature ranges and coefficient sets. The <Data></Data> block can be
used to input data points directly.

The unit for temperature is K. The unit used for the temperature dependent properties
(fitted polynomials functions) are defined in the table below:
TABLE 9-3: UNIT FOR TEMPERATURE-DEPENDENT PROPERTIES.

PROPERTY UNIT

Liquid density mol/m3

Ideal heat capacity J/mol/K
Ln vapor pressure 1
Heat of vaporization J/mol
Vapor viscosity Pa·s
Ln liquid viscosity 1
Vapor thermal conductivity W/m/K
Liquid thermal conductivity W/m/K
Surface tension N/m

Species Property References

All references used for the included constants and temperature-dependent properties
are available in the database file. In the xml file these are defined with the in line tag
Comment for constants. For example the critical pressure of methane is defined as

656 | CHAPTER 9: THERMODYNAMICS

 <CriticalPressure Comment="Twu C.H. et al. Fluid Phase Equilibria
105 (1995) 49-59.">4604005.35</CriticalPressure>.

citing the work of Twu and others(Ref. 8).

For temperature-dependent properties a separate <Comment></Comment> block is

used.

The reference comments can be inspected in the settings window by right-clicking a

species property node (under a Thermodynamic System) and selecting Properties.

Thermodynamic Properties Definitions

The thermodynamic properties provided are listed as species and mixture property in
a Property package.

Ideal Gas
The ideal gas law is independent of composition and determines V at given T and P.
Density can be calculated from

1
 = ---- (9-101)
V

The partial fugacity coefficients

ln ̂ i = 0 (9-102)

The ideal gas enthalpy for mixture

 T 
 xi  Hi ig T T
H ig = + C P i ig dT (9-103)
ref
ref 
i

where Hi,ig,Tref relates the enthalpy of an ideal gas to the enthalpy at the selected
reference state for species i.

The ideal gas entropy for species i

 T C P i ig 
- dT – R ln  --------
P -
S ig =  xi  Si ig T ref
– R ln x i + T ref
-----------------
T   P ref (9-104)
i

where Si,ig,Tref is the entropy of an ideal gas to the entropy of species at the selected
reference state.

The Gibbs free energy follows from

THERMODYNAMIC MODELS AND THEORY | 657

 G ig = H ig – TS ig (9-105)

Equation of State
The equation of state determines V at given x, T, and P. Density can be expressed as
Equation 9-101. The partial fugacity coefficients are derived from

P
ˆ
0  Vi – --------
1 RT
ln ̂ i = -------- (9-106)
RT P

where Vi is the partial molar volume. The enthalpy, entropy, and Gibbs free energy
follow from the partial fugacity coefficients and the ideal gas contributions as:

 ln ̂ i
H = H ig – RT 2  xi  -------------
T 
- (9-107)
i

 ln ̂ i
S = S ig – R  xi  ln ̂i + T -------------
T 
- (9-108)
i

G = G ig – RT  xi ln ̂i (9-109)
i

Heat Capacity

Heat capacity at constant pressure is calculated from

H
C P =  -------- (9-110)
T P,x

It is available when enthalpy is available. Heat capacity at constant volume is defined by

H
C v =  -------- (9-111)
T v,x

The relationship between heat capacity at constant pressure and constant volume can
be expressed as:

V P
C p – C v = T  -------  ------- (9-112)
T P,x T v,x

were v is a function of T and P. A Taylor expansion of vat constant composition gives

658 | CHAPTER 9: THERMODYNAMICS

 V V
v =  ------- T +  ------- P = 0 (9-113)
T P,x P T,x

Rearranging equations above gives

V 2
T  -------
T P,x
C v = C P + ------------------------ (9-114)
 V
-------
 P T,x

Cv is available if Cp and volume are available and fluid is compressible by means of

volume is pressure dependent. For ideal gas Equation 9-112 express as

Cp – Cv = R (9-115)

Specific heat capacity ratio is defined as

Cp
 = ------- (9-116)
Cv

Activity Coefficient Models

The enthalpy, entropy, and Gibbs free energy follow from the activity coefficients and
the ideal gas contributions in Equation 9-103 – Equation 9-105. The activity
coefficients describe the deviation of chemical potentials from the ideal liquid phase,
so heats of vaporization need to be accounted for

 2  ln  i
T
H =  xi  Hi ig T ref
+ T ref
C P i ig dT – H i vap – RT --------------
T
(9-117)
i
2  ln ̂ i sat
– R T ------------------------
T 

 T C P i ig P i sat
------------------ dT – R ln  --------------
S =  xi  Si ig T ref
– R ln x i + T ref
T  P ref 
- (9-118)
i
 ln  i  ln ̂ i sat H i vap
+ ln  i + T -------------- + ln ̂ i sat + T ------------------------ + R ---------------------
T T T 

THERMODYNAMIC MODELS AND THEORY | 659

  T 
G =  x i  H i ig T ref +
 T ref
C P i ig dT – T  S i ig T ref +

(9-119)
i
T C P i ig  Pi sat  
- dT + RT  ln x i + ln  i + ln ̂ i sat + ln --------------
 T ref
-----------------
T   P ref  
- 

Note that if the vapor phase is ideal, then the saturated fugacity,  i sat , contribution
can be ignored.

Other Properties
Partial fugacity is calculated from

fˆi = x i ̂ i P (9-120)

Internal energy is calculated from

U = H – PV +  xi Ui ig ref (9-121)

i

where Ui,ig,ref is the enthalpy of an ideal gas to the species enthalpy at the selected
reference state.

Helmholts energy is calculated from

A = U – TS = G – PV (9-122)

K-values for phases p and q are taken from

̂ i q
K i p q = --------- (9-123)
̂ i p

If only liquid phases are defined, the K-value calculation is reduced to

 i q
K i p q = --------- (9-124)
 i p

 xi Mi
M mix = (9-125)
i

660 | CHAPTER 9: THERMODYNAMICS

Standard Enthalpy of Formation and Absolute Entropy Terms
Formation terms are not included in the enthalpy, entropy, or the internal energy. If
the enthalpy of formation is specified for all species, EnthalpyF (HF) represent the
enthalpy including the formation terms. If the absolute entropy of all species are
specified then the EntropyF (SF) includes the absolute entropy.

At reference conditions, the heat of any reaction relates to the heat of formation as

H reac ref =  i  Hf ref  (9-126)

i

Note that for reacting flow or a heat balance in a reactor when the heat of reaction is
explicitly taken into account, the enthalpy should not include the heat of formation.

The following enthalpy expression should be used:

HF = H +  xi Hf i ref (9-127)

i

Hf,i,ref is calculated such that it matches the reference state of the package, even if the
species have a different reference state. Similarly, the absolute entropy of each species
is taken into account according to

SF = S +  xi Sabs i (9-128)
i

The entropy balance over a process that includes reactions should include either the
entropy of reaction and use S, or use SF without entropy of reaction.

In database, a set of parameters introduced to define Absolute entropy and Standard

enthalpy of formation for ideal gas and different phases (Vapor, liquid, Solid, and
Aqueous infinite dilution). One can use these parameters to calculate Gibbs free energy
of reaction when different phases are available (See Electrode reaction).

SPECIES GIBBS FREE ENERGY OF FORMATION

As the COMSOL ThermoDB does not include entropy of formation of species,
entropy Equation 9-128 and in consequence Gibbs free energy Equation 9-109 are
estimated from absolute entropy’s value. Therefore, the absolute value of entropy of
formation and Gibbs free energy of formation of the species are not correct. However,
for our applications these absolute values are not required while the value of entropy
and Gibbs free energy change of reaction (the difference value) are correct.

THERMODYNAMIC MODELS AND THEORY | 661

 If user needs the absolute value of entropy of formation, it is possible to estimate it by:

S i = S f i =  j Sabs j (9-129)
j

where the entropy of formation of species i is calculated from its elemental constituent
j. For example, entropy of formation of ammonia at 298 K is

N 2  g  + 3H 2  g   2NH 3 (9-130)

S f NH3 = 2S abs NH3 –  S abs N2 + 3S abs H2  (9-131)

The values from RHS of Equation 9-131 can be extracted from

COMSOLThermoDB. This value should be used in Equation 9-127 to estimate the
absolute value of Gibbs free energy of species.

Reference State
The reference temperature, pressure and phase can be specified for each package and
for species within a package. The reference phase can be a real phase or an ideal gas. If
a reference temperature, pressure, or phase is unspecified for a particular species, the
package reference temperature, pressure, or phase is used for that species.

The reference values for enthalpy, Hi,ref, entropy, Si,ref, and internal energy, Ui,ref, are
calculated so that the pure species enthalpy, entropy, and internal energy are equal to
zero at reference conditions.

The reference values for enthalpy, including formation terms, and entropy, including
absolute terms, are calculated such that the corresponding property for pure species i
has a value equal to the specified formation term at the species reference conditions.

Transport Properties
This section includes definitions of the models available in for thermal conductivity,
viscosity, and diffusivity:

• Thermal Conductivity
• Viscosity
• Diffusivity

662 | CHAPTER 9: THERMODYNAMICS

THERMAL CONDUCTIVITY

Vapor

Ideal

The thermal conductivity correlations is according to:

 xi i v + v P
v = (9-132)
i

The pressure correction v,P is calculated from the method of Stiel and Thodos, see
Ref. 32, which is applicable for r<3, but is less accurate for H2, strongly polar gases,
and gases with a high degree of hydrogen bonding, such as H2O and NH3

P c2 / 3
 v P = ----------------------------- A  exp   B r  + C   (9-133)
MT c1 / 6 Z c5


 r = ----- (9-134)
c

1
 c = ------ (9-135)
Vc

The mixing rules are as suggested by Yorizane, see Ref. 33:

 xi  xj Vc i j
Vc = (9-136)
i j

 xi  xj Vc i j Tc i j (9-137)

i j
T c = -----------------------------------------------------
-
Vc

 xi i
 = (9-138)
i

Z c = 0.291 – 0.08 (9-139)

RT c Z c
P c = ----------------- (9-140)
Vc

THERMODYNAMIC MODELS AND THEORY | 663

  xi Mi
M = (9-141)
i

where the binary constants are

1
V c i j = ---  V c1/i3 + V c1 /j3  3 (9-142)
8

T c i j = T c i T c j (9-143)

The Stiel and Thodos coefficients are

TABLE 9-4: PRESSURE CORRECTION PARAMETERS.

A B C
8
r0.5 A1=2.70210 B1=0.535 C1=-1
8
0.5r2.0 A2=2.52810 B2=0.670 C2=-1.069
8
r2.0 A3=0.57410 B3=1.155 C3= 2.016

However, in order to ensure 0th-order continuity at r  0.5 and r  2.0, the

following coefficients for   r  2.0 are recalculated from

A 1 C 1 + A 1 exp  0.5 B 1  – A 3 C 3 – A 3 exp  2.0 B 3 

A 2 = – ------------------------------------------------------------------------------------------------------------------------------- (9-144)
exp  2.0 B 2  – exp  0.5 B 1 

A 1 C 1 exp  2.0 B 2  + A 1 exp  0.5 B 1  exp  2.0 B 2 

C 2 = – ------------------------------------------------------------------------------------------------------------------------------- (9-145)
A 1 C 1 + A 1 exp  0.5 B 1  – A 3 C 3 – A 3 exp  2.0 B 3 
A 3 C 3 exp  2.0 B 2  + A 3 exp  0.5 B 2  exp  2.0 B 3 
– -------------------------------------------------------------------------------------------------------------------------------
A 1 C 1 + A 1 exp  0.5 B 1  – A 3 C 3 – A 3 exp  2.0 B 3 

The vapor thermal conductivity correlation must be available for all species. Also
critical volumes, Vc,i, critical temperatures, Tc,i, molecular weights Mi, and acentric
factors i must be specified for all species.

Kinetic Theory

Lindsay and Bromley (see Ref. 34) provided an equation for the interaction parameters
of the method of Wassiljewa (see Ref. 35) based on the kinetic theory, to provide
mixture thermal conductivity from pure species values

664 | CHAPTER 9: THERMODYNAMICS

  
 x 
 ------------------------
i i v 
v =  
- +  v P

(9-146)
i

 x j  i j

j

2
 T + 3   
 --- T   9
 T +  --4- T b i T b j
1  i v  M j 3 / 4   2 b i 
 i j = --- 1 + ---------- -------  ------------------------------   ---------------------------------------------- (9-147)
4  j v  M i   3   
 T +  --- T b i 
3
  T +  --2- T b j 
   2 

where the pressure correction v,P is calculated from Equation 9-133. Both vapor
thermal conductivity correlation i,v and the vapor viscosity correlation i,v must be
available for all species. In addition, all normal boiling points Ti,b, molecular weights
Mi, critical volumes Vc,i, critical temperatures Tc,i, and acentric factors i must be
specified.

Water (IAPWS)

The International Association of the Properties of Water and Steam recommend an

equation Ref. 36 which is valid in the following range:

273.15 K  T  773.15 K p  100 MPa (9-148)

773.15 K  T  923.15 K p  70 MPa (9-149)

923.15 K  T  1073.15 K p  40 MPa (9-150)

Liquid
The following mixture models are available for liquid thermal conductivity

Ideal

To calculate the mixture liquid thermal conductivity, l,m, the values of pure liquid
thermal conductivity correlations are mixed ideally

 x i  i l
 l m = (9-151)
i

The pressure dependence is based on the work of Missenard (Ref. 52) where

 l m  P
----------------- = 1 + QP r0.7 (9-152)
 l m

THERMODYNAMIC MODELS AND THEORY | 665

 where Q is correlated as

Q = -0.013693477 + 0.057427673T r + 0.001617831  T r   ln P 1  (9-153)

and the following mixing rules are used

T
T r = ------ (9-154)
Tc

P
P r = ------ (9-155)
Pc

RT c Z c
P c = ----------------- (9-156)
Vc

 x i V c i
Vc = (9-157)
i

 x i T c i
Tc = (9-158)
i

 x i Z c i
Zc = (9-159)
i

All liquid thermal conductivity correlations must be specified. All values for critical
temperatures, Tc,i, critical volumes, Pc,i and critical compressibility factors, Zc,i must
be specified for all species i.

Power Law

The values of pure liquid vapor thermal conductivity correlations are mixed according
to the following power law

1 xi
-----------
 l2 m
=  --------
 l i
(9-160)
i

All liquid thermal conductivity correlations must be specified. The model is valid for
pure compound thermal conductivity values that are no more apart than a factor of 2
(Ref. 53 and Ref. 54). The pressure dependence is introduced using Equation 9-152
through Equation 9-159. All values for critical temperatures, Tc,i, critical volumes, Pc,i
and critical compressibility factors, Zc,i must be specified for all spices i.

666 | CHAPTER 9: THERMODYNAMICS

Local Composition

The local composition model by Rowley (Ref. 54) uses an ideal and excess
contribution

 l m =  l ideal +  l excess (9-161)

The ideal part is based on mass fractions

 l ideal =  i i l (9-162)

i

xi Mi
 i = -------------------- (9-163)
xj Mj
j

The excess term is based on NRTL local concentrations

  i j Gj i  j i – i l 

 l excess = ------------------------------------------------------------------
i j - (9-164)

 j G j i
j

where Gj,i follows from Equation 9-57. The binary interaction terms follow from

 i  i i  i l +  j  j j  j l
 i j =  j i = -------------------------------------------------------- (9-165)
 i  i i +  j  j j

which is symmetric, and on the diagonal,

 i i =  i l (9-166)

and

 i i =  i   i +  j G j i  (9-167)

with i is the composition in the binary mixture of species i and j and the local
composition is equi-molar

M i G j i
 i = -------------------------------------------------- (9-168)
M i G j i + M j G i j

THERMODYNAMIC MODELS AND THEORY | 667

 All liquid thermal conductivity correlations must be specified. The pressure
dependence is introduced using Equation 9-152 – Equation 9-159. All values for
critical temperatures Tc,i, critical volumes Pc,i, critical compressibility factors Zc,i, and
molecular weights Mi must be specified for all compounds i. In addition, all NRTL
binary interaction parameters Ai,j must be specified. Unspecified values for NRTL
interaction parameters Bi,j are set to zero. The randomness parameters i,j have values
of zero on the diagonal and the matrix is symmetric. All off-diagonal values must be
specified. NRTL model is presented in Equation 9-53 to Equation 9-64.

Local Composition (Modified)

Rowley (Ref. 53) adapted the local composition model by replacing the mixing rule in
Equation 9-165 by the following

M i   i  i i  i l + M j   j  j j  j l
 i j =  j i = ---------------------------------------------------------------------------------- (9-169)
M i   i  i i  + M j   j  j j 

which he found to produce better model predictions in most cases where both the
Local Composition model and Power Law model have trouble. However, the model
is not as generally applicable; for instance, systems containing H2O are not well
described by this model due to the low molecular weight of H2O.

Water (IAPWS)

The International Association of the Properties of Water and Steam recommend an

equation Ref. 36 which is valid in the following range:

273.15 K  T  773.15 K p  100 MPa (9-170)

773.15 K  T  923.15 K p  70 MPa (9-171)

923.15 K  T  1073.15 K p  40 MPa (9-172)

VISCOSITY

Vapor

Wilke

Wilke, see Ref. 37, based his method for mixture viscosity of the vapor phase on kinetic
theory:

668 | CHAPTER 9: THERMODYNAMICS

  
 x  (9-173)
 ---------------------
i i v 
v =  
-

i
 
 x j  i j

j

2
  i v M j 1 / 4
 1 + ----------  -------- 
  j v Mi 
 i j = ------------------------------------------------------ (9-174)
Mi
8  1 + -------
 M j

The vapor viscosity correlation i,v must be available for all species. In addition, all
molecular weights Mi must be specified.

Brokaw

Brokaw (see Ref. 38) uses the same basic equation as Wilke (Equation 9-173).
However, Equation 9-174 is replaced by

 i v
 i j = S i j A i j ---------
- (9-175)
 j v

and the interaction parameter is defined as

 
 i j  RM i j – RM i0.45 j


A i j = --------------------  1 + ----------------------------------------------------------------------------------------- (9-176)
RM i j  1 + RM i0.45 
j
2  1 + RM i j  + ------------------------------------------------
     1 + RM 
i j i j

where

 4M i M j  1 / 4 Mi
 i j =  ----------------------------2 , RM i j = ------- (9-177)
  Mi + M   Mj
j

The vapor viscosity correlation, i,v must be available for all species i. In addition, all
molecular weights Mi must be specified. If Lennard-Jones energy i (see Ref. 39)
Stockmayer’s polar parameter s,i(Ref. 40 and Ref. 41) are specified for both species i
and j then

THERMODYNAMIC MODELS AND THEORY | 669

 T 2- + 1 ---  
1 + --------
 i  j 4 s i s j
S i j = ---------------------------------------------------------------------------
- (9-178)
T 1 T 1
1 + ---- + ---  s i 1 + ---- + ---  s j
i 4 j 4

Otherwise,

S i j = 1 (9-179)

High Pressure Modification

To account for the effect of pressure on vapor viscosity, a pressure correction can be
applied. The pressure dependence is based on kinetic gas theory, which adds the
following term to the vapor viscosity:

 M t P c2 / 3  10 – 7
- --------------------------- 
 v P =  ----------------------- (9-180)
 T c1 / 6   101325 2 / 3 

where is calculated from the correlation of Jossi (Ref. 42), which is applicable for
r  3.0. It is less accurate for H2, strongly polar gases and gases with a high degree of
hydrogen bonding such as H2O and NH3.

The correction factor is due to using pressure, atm, and viscosity, cP, units in Jossi’s
correlation. It is expressed as:

1
---
4
 + 1 = 1.0230 + 0.23364 r + 0.58533  r2 (9-181)

– 0.40758  r3 + 0.093324  r4


 r = ----- (9-182)
c

1
 c = ------ (9-183)
Vc

The following mixture rules are used

RT c Z c
P c = ----------------- , V c =
Vc  x i V c i , T c =  x i T c i (9-184)
i
i

670 | CHAPTER 9: THERMODYNAMICS

  x i Z c i  xi Mi
Zc = ,M = (9-185)
t
i i

The values for critical volumes, Vc,i, critical temperatures, Tc,i, critical compressibility
factors, Zc,i and molecular weights, Mi must be specified for all species i.

The high pressure correction is available for the Wilke and Brokaw mixture models.
The vapor viscosity follows from

 v =  v Wilke +  v P (9-186)

where v,Wilke is calculated from Equation 9-173.

Pedersen Corresponding States Model

The corresponding states viscosity model of Pedersen (Ref. 43 and Ref. 44) applies to
both vapor and liquid phases of hydrocarbon mixtures. The selected reference species
is CH4.

The CH4 viscosity is calculated from Ref. 45, modified by Pedersen and Fredunsland
(Ref. 46) to avoid issues below 91 K where CH4 becomes solid

 CH =  CH 4 0 +  CH 4  CH  1 + F 1  CH  2 + F 2  CH  3 (9-187)
4 4 4 4

where

H+1
F 1 = -------------- (9-188)
2

1–H
F 1 = -------------- (9-189)
2

exp  T  – exp  – T 
H = ------------------------------------------------------------- (9-190)
exp   T  + exp  – T  

T = T – 91 T  K (9-191)

Here, CH4 is used in g/cm3; for the mass-mole conversion of CH4, a molecular
weight of MCH4 = 16.042568 g/mol is used.

The dilute gas part is given by

THERMODYNAMIC MODELS AND THEORY | 671

 –L1 L2 L3
 CH4 0 = ---------- + -----------
/
– ----------- (9-192)
T T 2 3 T1 / 3
+ L4 –L5 T 1 / 3 + L6 T 2  3 – L7 T + L8 T 4  3 – L9 T 5 / 3

The first density correction for the moderately dense gas is given by

T 2
 CH4 1 = L 10 – L 11  1.4 – ln ---------- (9-193)
168

The remainder is given by the empirical correlation

L 12   L 15 
 CH4 2 = exp  --------- – L 13  exp   10  CH4   L 14 – ----------- + (9-194)
 T    T 3 / 2
  CH –  c CH4 L 17 L 18  
4 -   CH   L 16 + --------
 ------------------------------------ - + ---------  – 1
 4  T 2 
 c CH 4  T  

The correction term for solid CH4

L 19 L 22 
 CH4 3 = exp  --------- – L 20  exp   10  CH 4   L 21 – -----------
 T    T 3 / 2 (9-195)
 CH 4 –  c CH 4 L 24 L 25 
+  -----------------------------------
-   CH   L 23 + --------
 4 
- + --------- – 1
 c CH T T2   
4

with the values of the parameters L1 through L25 are listed in Table 9-5 below:
TABLE 9-5: METHANE VISCOSITY NUMERICAL COEFFICIENTS.

L1 2.090975·105 L10 1.696985927 L19 9.74602

5
L2 2.647269·10 L11 0.133372346 L20 44.6055
5
L3 1.472818·10 L12 188.73011594 L21 18.0834
L4 47167.40 L13 10.35060586 L22 4126.66
L5 9491.827 L14 17.571599671 L23 0.976544
L6 1219.979 L15 3019.3918656 L24 81.8134
L7 96.27993 L16 0.042903609488 L25 15649.9
L8 4.274152 L17 145.29023444
L9 0.08141531 L18 6127.6818706

Here, CH4 is used in g/cm3; the critical density is given by c,CH4  0.16284 g/cm3.
The following equation by McCarty (Ref. 47) is solved for the density of CH4

672 | CHAPTER 9: THERMODYNAMICS

  N 5 N 6
P = N 1  CH T +  CH
2
 – N 2 T + N 3 T – N 4 + ------- – ------2- (9-196)
4 4
 T T 
 N 9 N 10  – N T + N + –------------ N 13
+  CH
3  N 7 T – N 8 + ------- – --------- - +  CH 4 - + N 14  CH 5
 T 2  11 12 T 
T 
4 4 4

 N 15 N 16  CH7
 N 18 N 19  CH9
+  CH ---------- + ---------- + N 17 ------------- +  CH
4 4
6  – 8  ---------- + ---------- + N 20 -------------
4
 T T 
2 T 4
 T T 
2 T
 3  N 22 N 23  N 24 N 25  N 26 N 27
+ exp  – N 21  CH
2    CH 2
- – ---------- +  CH
 --------- 3
5
2
- + ---------- +  CH
 --------- 4
7  ---------
- + ----------
4
 4
T T 
4
T T 
4
 T2 T 
3

 N 28 N 29  N 30 N 31  N 32 N 33 4 
+  CH
9
2
- – ---------- +  CH
 – --------- 4 2
- + ---------- +  CH
11  – ---------
3
13  ---------
2
- – ---------- + N 34 T  
3
4
 T T 
4
 T T 
4
T T 

where CH4 is used in mol/l.

TABLE 9-6: COEFFICIENTS IN THE FUNCTIONAL FORM OF THE MCCARTY EOS.

N1 0.08205616 N13 2.8685285973 N25 1.6428375992·106

N2 0.018439486666 N14 0.11906973942·10-3 N26 0.21325387196
N3 1.0510162064 N15 0.0085315715699 N27 37.791273422
N4 16.057820303 N16 3.8365063841 N28 0.1185701681·10-4
-4
N5 848.44027562 N17 0.24986828379·10 N29 31.630780767
-5
N6 42738.409106 N18 0.57974531455·10 N30 0.4100678294·10-5
N7 0.76565285254·10-3 N19 0.0071648329297 N31 0.0014870043284
-3
N8 0.48360724197 N20 0.12577853784·10 N32 3.151226153·10-9
N9 85.195473835 N21 0.0096 N33 0.2167077474·10-5
N10 16607.434721 N22 22240.102466 N34 0.2400055107·10-4
N11 0.37521074532·10-4 N23 1.4800512328·106
N12 0.028616309259 N24 50.498054887

With the viscosity and density of CH4 defined, the viscosity of any mixture, mcan be
calculated from the corresponding states principle

–1
Tc ------ Pc 2 / 3 Mm 1 / 2 
 m =  ------------------ 6  -----------------  ---------------  -------------  CH4 P 0 T 0 (9-197)
 T c CH   P c CH   M CH    CH 
4 4 4 4

where CH4 viscosity CH4,P0,T0 is calculated at temperature, T0 and pressure P0

THERMODYNAMIC MODELS AND THEORY | 673

 T c CH  CH
T 0 =  ------------------4 T  -------------4 (9-198)
Tc 

P c CH  CH
P 0 =  -----------------4 P  -------------4 (9-199)
 Pc    

The following mixing rules are used for the critical properties, see Ref. 48:

  x i x j  i j T c i T c j
(9-200)
i j
T c = -----------------------------------------------------------
-
 x i x j  i j
i j

8   x i x j  i j T c i T c j
(9-201)
i j
--------------------------------------------------------------
-
Pc =
 2

   xi xj i j
i j

T c i 1 / 3  T c j 1 / 3 3
 i j =   ---------- +  ----------  (9-202)
P c i P c j

The parameter  is

–3 0.5173
 = 1 + 7.378 10  r1.847 M m (9-203)


CH 4 P 0 T 0
 r = --------------------------
- (9-204)
 c CH4

where

T c CH
T 0 =  ------------------4 T (9-205)
Tc

P c CH
P 0 =  -----------------4 P (9-206)
 Pc 

with c,CH4  0.16284 g/cm3. For CH4

–3 0.5173
 CH 4 = 1 + 7.378 10  r1.847 M CH 4 (9-207)

674 | CHAPTER 9: THERMODYNAMICS

where Equation 9-204 is used. The mixture molecular weight is a function of the
weight-averaged molecular weight and the number-averaged molecular weight

–4 2.303 2.303
M m = 1.304 10  M W – MN  + MN (9-208)

 xi Mi
2

i (9-209)
M W = --------------------
-
MN

 xi Mi
MN = (9-210)
i

where the power in Equation 9-208 is determined by fitting to experimental viscosity

data.

Note that pure species vapor viscosity correlations i,v are not required. However, for
each species i, molecular weight Mi, critical temperature, Tc,i and critical pressure, Pc,i
must be specified.

Water (IAPWS)

The International Association of the Properties of Water and Steam recommend an

equation Ref. 49- Ref. 50 for industrial application which is valid in the following
range:

273.16K  T  1173.15K 0  p  pt (9-211)

T m  p   T  1173.15 K p t  p  300 MPa (9-212)

T m  p   T  873.15 K 300 MPa  p  350 MPa (9-213)

T m  p   T  433.15 K 350 MPa  p  500 MPa (9-214)

T m  p   T  373.15 K 500 MPa  p  1000 MPa (9-215)

where T m is the pressure dependent melting temperature and p t is the triple-point

pressure. In accordance with industrial application recommendations, critical region
correction is not applied.

Liquid
The following mixture models are available for liquid viscosity.

THERMODYNAMIC MODELS AND THEORY | 675

 Molar Logarithmic Mixing

The values of pure species log liquid viscosity, ln i,l are mixed ideally using mole
fractions xi

ln  l m =  xi ln i l (9-216)
i

where m,l is the mixture viscosity of liquids.

Mass Logarithmic Mixing

The values of pure species log liquid viscosity correlation are mixed ideally using the
weight fractions i

 i ln i l
ln  l m = (9-217)
i

Pedersen Corresponding States Model

The Pedersen Corresponding States Model described above for the gas phase viscosity
also applies to the liquid phase. Pure species liquid viscosity correlations are not
required. However, for each species i, molecular weight Mi, critical temperature Tc,i,
and critical pressure Pc,i, must be specified.

Cubic mixing

The mixture viscosity is defined using the cubic root average in terms of the mole
fractions xi

 3
 l m = 
  x i  i1 /l3

(9-218)
i

The model is noted in Ref. 51 to provide reasonable results for hydrocarbon mixtures
of similar components.

The model requires that the log liquid viscosity correlation is available for all species i.

Cubic mass mixing

The mass fraction equivalent of the previous model is

 3
 l m = 
   i  i1 /l3

(9-219)
i

676 | CHAPTER 9: THERMODYNAMICS

The model requires that the log liquid viscosity correlation is available for all species i.

Water (IAPWS)

The International Association of the Properties of Water and Steam recommend an

equation Ref. 49- Ref. 50 for industrial application which is valid in the following
range:

273.16K  T  1173.15K 0  p  pt (9-220)

T m  p   T  1173.15 K p t  p  300 MPa (9-221)

T m  p   T  873.15 K 300 MPa  p  350 MPa (9-222)

T m  p   T  433.15 K 350 MPa  p  500 MPa (9-223)

T m  p   T  373.15 K 500 MPa  p  1000 MPa (9-224)

where T m is the pressure dependent melting temperature and p t is the triple-point

pressure. In accordance with industrial application recommendations, critical region
correction is not applied.

DIFFUSIVITY
Two types of diffusion coefficients are supported. Diffusion coefficients in infinitely
diluted systems, and Maxwell-Stefan diffusion coefficients.

For dilute systems, the binary diffusion coefficient D0i,j represent the diffusivity of
species i in a medium consisting of pure species j. This corresponds to the Fickian
diffusion coefficient.

For any mixture, the binary Maxwell-Stefan diffusion coefficient D i j , represents the
inverse drag coefficient of species i moving past species j (Ref. 55 - Ref. 58). This
property is referred to as the Maxwell-Stefan diffusivity. The Maxwell-Stefan diffusivity
is symmetric, D i j = D j i , and the diagonal elements D i i are not used. T

Gas Phase Diffusion Coefficient at Infinite Dilution

The following models are available for the diffusion coefficients at infinite dilution in
the vapor phase:

• Fuller Schettler Giddings

• Wilke-Lee

THERMODYNAMIC MODELS AND THEORY | 677

 Automatic When the Gas diffusivity property model is set to Automatic, the Fuller
Schettler Giddings model is used, provided that the Fuller diffusion volume is known
for both species (i and j), otherwise the Wilke-Lee model is used.

Fuller Schettler Giddings

Fuller et al. (Ref. 59) modified the Chapman-Enskog relation to correlate binary
diffusion coefficient for species i and j in the vapor phase according to the Fuller
Schettler Giddings (FGS) model:

– 2 1.75 1 1-
1.01325  10 T ------- + ------
0 Mi Mj
D i j = -------------------------------------------------------------------------------
1 1 2
- (9-225)
 --- ---
3  3
P   v +  v 
 
  
 i  
j

where T denotes the temperature (K), Mi the molecular weight of species i (g/mol)
and P is the pressure (Pa). vi are the atomic diffusion volumes (Fuller diffusion
volume), (cm3), which are estimated using group contribution for each species
(Ref. 60):
TABLE 9-7: ATOMIC AND STRUCTURAL DIFFUSION VOLUME INCREMENTS

GROUP CONTRIBUTION

C 15.9
H 2.31
O 6.11
N 4.54
F 14.7
Cl 21
Br 21.9
I 29.8
S 22.9
Aromatic Ring -18.3
Heterocyclic Ring -18.3

678 | CHAPTER 9: THERMODYNAMICS

For some simple molecules the below values, determined from regression, are used:
TABLE 9-8: DIFFUSION VOLUMES OF ATOM AND SIMPLE MOLECULES

SPECIES FULLER DIFFUSION

VOLUME

He 2.67
Ne 5.98
Ar 16.2
Kr 24.5
Xe 32.7
H2 6.12
D2 6.84
N2 18.5
O2 16.3
CO 18
CO2 26.9
N2O 35.9
NH3 20.7
H2O 13.1
SF6 71.3
Cl2 38.4
Br2 69
SO2 41.8
Air 19.7

Wilke-Lee

Wilke and Lee (Ref. 61) also modified the Chapman-Enskog relation to correlate
binary diffusion coefficient in vapor phase according to:

3.03 –  --------------------- T
0.98 1.5

0 –2 MW i j
D i j = 10  -------------------------------------------------------
2
- (9-226)
P i j  D MW i j

where

THERMODYNAMIC MODELS AND THEORY | 679

 2
MW i j = --------------------- (9-227)
1
------- + ------1-
Mi Mj

The length scale  i j for the interaction is taken from the Lennard-Jones diameter
parameters of species i and j:

LJ LJ
 i + j 
 i j = ------------------------------- (9-228)
2
LJ
If  i is not specified in the database, it is instead estimated from:

1
---
LJ –8 3
i = 1.18  10 V i l b (9-229)

where Vi,l,b is the molar volume of species at normal boiling point.

The collision integral  D is evaluated from (Ref. 62):

-0.15610
 D = 1.06036 T + 0.19300 exp  -0.47635 T  (9-230)
+ 1.03587 exp  -1.52996 T  + 1.76474 exp  -3.89411 T 

with

T
T = -------- (9-231)
 i j

The energy scale  i j for the interaction is taken from the Lennard-Jones energy
parameters of species i and j:

LJ LJ
 i j = i j (9-232)
LJ
If  i is not specified in the database, it is instead estimated from:

LJ
i
--------
- = 1.15T i l b (9-233)
k

where k is the Boltzmann constant, and T i l b is normal boiling point temperature.

Gas Phase Maxwell-Stefan Diffusivity

For gas phase diffusion the Maxwell-Stefan diffusivities are defined from the models
for gas phase diffusivity at infinite dilution

680 | CHAPTER 9: THERMODYNAMICS

 0
D i j = D i j i  j (9-234)

All models for gas phase diffusion at infinite dilution are symmetric, the diffusivity of
species i in species j equals that of species j in species i. In addition, under the ideal gas
assumption, the Maxwell-Stefan diffusion coefficient matches the Fick diffusion
coefficient. This implies that the Maxwell-Stefan gas diffusivities provided are
independent of composition.

Liquid Phase Diffusion Coefficients at Infinite Dilution

The following models are available for the diffusion coefficients at infinite dilution in
liquid phase:

• Wilke-Chang
• Tyn-Calus
• Hayduk-Minhas
• Siddiqi-Lucas
• Erkey-Rodden-Akgerman

Automatic When the Liquid diffusivity at infinite dilution property model is set to
Automatic, a selection for each solute i in solvent j will be made from the models
according to the following rules. Except in the case of a temperature correlation and
the Erkey-Rodden-Akgerman model, all of these rules require that the log liquid
viscosity correlation, ln j is available in the database for species j and that the liquid
volume at normal boiling point, Vi,l,b is available for the species i.

• If a temperature correlation is available for species i and j, it is used.

• If the solvent is water, the Siddiqi-Lucas correlation (for aqueous systems) is used.
• If the solute and solvent are both normal paraffins, the Hayduk-Minhas correlation
(for normal paraffins) is used.
• If the solvent is a normal paraffin, and the liquid density correlation for the solvent
is available, and the solute is hydrogen, carbon-monoxide or carbon-dioxide, the
Erkey-Rodden-Akgerman correlation (for normal paraffins) is used.
• If parachors Pi and Pj are both available, and the liquid volume at normal boiling
point, Vi,l,b is available for the solvent, the Tyn-Calus correlation is used.
• If parachors Pi and Pj are both available, the Hayduk-Minhas correlation is used.
• If the solute and solvent are both organic molecules and the liquid volume at normal
boiling point, Vi,l,b is available for the solvent, the Siddiqi-Lucas method is used.

THERMODYNAMIC MODELS AND THEORY | 681

 • If the molecular weight Mj is available for the solvent, the Wilke-Chang correlation
is used.
• If the solvent is a normal paraffin, and the liquid density correlation for the solvent
is available, and the solute is a normal paraffin, the Erkey-Rodden-Akgerman
correlation (for normal paraffins) is used.
• If the solvent is a normal paraffin, and the liquid density correlation for the solvent
is available, and the Lennard-Jones diameter for the solute is available, the
Erkey-Rodden-Akgerman correlation (for normal paraffins) is used.

For the Siddiqi-Lucas method, a molecule is considered organic if it has at least one C
atom bound to anything else than O or C atoms. This is determined by the SMILES
formula, if available. If, for any pair of species, the required input data for none of the
above models is available, the entire property liquid diffusion coefficient at infinite
dilution is not available.

Wilke-Chang

The correlation by Wilke and Chang (Ref. 63) for liquid phase diffusion coefficients at
infinite dilution is:

0 – 18 T j Mj
D i j = 1.858795959  10 --------------------
0.6
- (9-235)
 j V i l b

Molecular weight, Mj and log liquid viscosity correlation, ln  j , for species j and liquid
molar volume at normal boiling point for species i, V i l b , is required. The
Wilke-Chang association parameter  j , if unavailable, is set to:
TABLE 9-9: ASSOCIATION PARAMETERS FOR SOLVENT

SOLVENT ASSOCIATION
PARAMETER

Water 2.26 (Ref. 64)

Methanol 1.9
Ethanol 1.5
Others 1

Species are identified by their CAS number or SMILES formula. The Wilke-Chang
correlation is not suitable for diffusion of water. If water is the solute, the correction
suggested by Kooijman (Ref. 65) is applied where liquid molar volume of water at
normal boiling point, Vwater,l,b is multiplied by 4.5.

682 | CHAPTER 9: THERMODYNAMICS

Tyn-Calus

The Correlation by Tyn and Calus (Ref. 66) for liquid diffusion coefficients at infinite
dilution reads:

1
 --6-  0.6
T  V i l b P j
0 – 16  
D i j = 8.93  10 ------------------------------------- (9-236)
1
 --3-  0.6
 j  V j l b P i
 

The log liquid viscosity correlation ln  j should be available for species j, The liquid
volume at normal boiling point, Vi,l,b and parachor, Pi should be available for both
species i and j.

If the solvent is nonpolar (dipole moment is zero), and the solvent is methanol, ethanol
or1-butanol or if the solvent is a mono-hydroxy alcohol, both the liquid volume at
3
normal boiling point, Vj,l,b and the parachor, Pj are corrected by a factor of 8  10  j .

If the solute is water, both the liquid volume at normal boiling point, Vi,l,b and
parachor, Pi for the solute are corrected by a factor 2. This factor also applies if it is
detected from the SMILE formula that the species is an organic acid (a carboxyl group
is found), except in the cases where the solvent is water, methanol or n-butanol.

Hayduk-Minhas

Hayduk and Minhas (Ref. 67) suggested three different correlations for liquid
diffusion coefficients at infinite dilution.

Aqueous Solutions: in case the solvent is water (derived from CAS number or SMILES
formula), the correlation reads:

0 – 12 1.52  0.07244359601 
D i j = 1.25  10 T  ------------------------------------------ – 0.292 (9-237)
 0.19
V i l b 
9.58  10 -
–6
 --------------------------- – 1.12
3  V i l b
   j  10 

Normal paraffin solutions: In case both the solute and solvent are normal paraffins
(derived from SMILES formula), the correlation reads:

THERMODYNAMIC MODELS AND THEORY | 683

 10.2  10
–6
 ---------------------------- – 0.791
  
    10 3  Vi l b 
– 16 1.47  j
---------------------------------------------------------------------
0
D i j = 7.30889362  10 T (9-238)
 0.71 
 V i l b 
 

For all other systems, the correlation is:

1.29
0 – 16 T Pj
D i j = 3.8934239  10 ---------------------------------------------
0.92 0.23 0.42
- (9-239)
 j  V j l b P i

If the solvent is nonpolar (dipole moment is zero), and the solvent is methanol, ethanol
or1-butanol or if the solvent is a mono-hydroxy alcohol, both the liquid volume at
3
normal boiling point, Vj,l,b and the parachor, Pj are corrected by a factor of 8  10  j .

If the solute is water, both the liquid volume at normal boiling point, Vi,l,b and
parachor, Pi for solute are corrected by a factor 2. This factor also applies if it is
detected from the SMILES formula that the species is an organic acid (a carboxyl
group is found), except in the cases where the solvent is water, methanol or n-butanol.

Siddiqi-Lucas

Siddiqi and Lucas (Ref. 68) suggested correlations for liquid diffusion coefficients at
infinite dilution for aqueous system (including gases) and for organic solutions. For
normal paraffins systems, they recommended the Hayduk-Minhas model.

For aqueous solutions:

0 – 17 T
D i j = 1.295436901  10 --------------------------------------
1.026 0.5473
- (9-240)
j  V i l b 

For all other systems, the equation for organic solution is used as:

0.265
0 – 15 T  V j l b 
D i j = 1.459473761  10 ----------------------------------
0.907 0.45
- (9-241)
j  V i l b 

Where T is temperature, Vi,l,b is liquid volume at normal boiling point and  j is the
viscosity of the solvent.

Erkey-Rodden-Akgerman

684 | CHAPTER 9: THERMODYNAMICS

The correlation by Erkey et al. (Ref. 69) for liquid diffusion coefficients at infinite
dilution in normal paraffins is:

ref 6
0 –9 T  V – V j  10
D i j = 94.5  10 ------------------------------------------------------------------------------------ (9-242)
0.239 0.781 – 20 1.134
Mi Mj   i  j  10 

where the reference volume is

ref 1 3
Vj = ------- b j N Av  j (9-243)
2

NAv is Avogadro’s number, and the deviation from closest packing volume is given by

i
b j = 1.206 + 0.0632  ----- (9-244)
j

The correlation is fitted to normal paraffins, hydrogen, carbon monoxide and carbon
dioxide diffusing in normal paraffins. The molecular weight Mi should be available for
both solute and solvent. The Lennard-Jones diameter, i is estimated from Bondi
group contribution method (Ref. 70), and for some species are taken from Ref. 69 and
Ref. 71 as:
TABLE 9-10: MOLECULAR DIAMETERS FOR SPECIES
10
SPECIES   10 (M)

H2 2.92
CO 3.72
CO2 3.97
1/3
n-CjH2j+2 (21.82+32.44*j)

To prevent the diffusion coefficients from becoming negative, the minimum difference
of (V  Vjref) is considered to be 1012 mol/m3.

Liquid Phase Maxwell-Stefan Diffusivity

The Maxwell-Stefan liquid diffusion coefficients are calculated from the liquid
diffusion coefficients at infinite dilution. The diagonal values should be ignored and
are set to zero. The Vignes (Ref. 72) model for diffusion in binary solutions can be
extended to multi-component systems (Ref. 73):
n

 Di j x  1 
xk
D i j = k
(9-245)
k=1

THERMODYNAMIC MODELS AND THEORY | 685

 where D i j xk  1 denotes the Maxwell-Stefan liquid diffusion coefficient for species i
and j in the limited of pure species k. If k=j, it represents a binary system of species i
and j where i is infinitely diluted. In addition, at infinite dilution the thermodynamics
factor (activity) (Ref. 58) becomes unity and the Maxwell-Stefan diffusivity equals to
Fick diffusivity:

0 0
D i j x j  1 = D i j = D i j (9-246)

Similarly,

0 0
D i j xi  1 = D j i = D j i (9-247)

Models for the D i j x k  1 for k  i and k  j remain to be defined in such a way that
symmetry is ensured:

D i j = D j i (9-248)

and to ensure continuity if both species i and j vanish:

lim D i j x k  1 = lim D i j x k  1 (9-249)

xi  0 xj  0

For binary systems, Equation 9-245 reduces to the Vignes interpolation formula.

Wesseling-Krishna

Wesseling and Krishna (Ref. 73) proposed:

0 0
D i j xk  1 = D i j D j i (9-250)

leading to:

0  1 + xj – xi   2 0  1 + xi – xj   2
D i j =  D i j   D j i  (9-251)

Kooijman-Taylor

Kooijman and Taylor (Ref. 74) found on a limited number of systems that this
provides better results:

0 0
D i j xk  1 = D i k D j k  k  i j  (9-252)

leading to:

686 | CHAPTER 9: THERMODYNAMICS

 n
0 xj 0 xi xk

0 0
D i j =  D i j   D j i  D i k D j k  (9-253)
k = 1
k  i j

Wesselingh and Bollen (Ref. 75) asserted that this is a reasonable estimate.

Krishna-van Baten

Krishna and van Baten (Ref. 76), on the basis of data obtained from molecular
dynamic simulations, proposed the following Vignes-based (Ref. 72) interpolation:

xi 
 -------------- xj 
 --------------
- -
 x i + x j  x i + x j
0 0
D i j x k  1 =  D i k   D j k   k  i j  (9-254)

The model reduces to the Kooijman-Taylor model for xi = xj. The value of D i j xk  1
is undefined in the limit of both x i  0 and x j  0 . From a physical point of view this
is inconsequential as the value cancels out in the expressions obtained for the fluxes
using the Maxwell-Stefan equations. Nevertheless, in order to obtain well-defined
values and composition derivatives of D i j x k  1 itself, the equation is modified to:

xi + x 
 ----------------------------- xj + x 
 -----------------------------
 x i + x j + 2 x  x i + x j + 2 x
0 0
D i j x k  1 =  D i k   D j k   k  i j  (9-255)
– 10
where  x = 10 is taken as a small composition. The limiting case for both
x i  0 and x j  0 also reduces to the Kooijman-Taylor model. This equation leads
to:

n xi + x
 ----------------------------- xj + x
 ----------------------------- xk
  x + x + 2 x  x i + x j + 2 x 
xj xi
  D0  i j 

0 0 0
D i j =  D i j   D j i   i k
 D j k 

(9-256)
k = 1 
k  i j

Surface Tension
Below the available surface tension models are presented.

THERMODYNAMIC MODELS AND THEORY | 687

 GAS-LIQUID SURFACE TENSION

Ideal
The gas-liquid surface tension is predicted by ideally mixing the pure species
correlations. It is independent of pressure, vapor temperature or composition.

 xi l i vl
 vl = (9-257)
i

where the vapor-liquid surface tension correlations, i,vl, must be specified for all
species i, and are evaluated at the temperature of the liquid phase.

Winterfeld
Following Winterfeld (Ref. 77), the vapor-liquid surface tension is predicted by mixing
the pure species correlations according to

x i l x j l  i vl  j vl
  ---------------------------------------------
 i l  j l
-
 vl = -------------------------------------------------------------
i j - (9-258)
 x i l 2

  i l-------- 
i

It is independent of pressure, vapor temperature and composition. The vapor-liquid

surface tension correlations and liquid density correlations must be specified for all
species i, and are evaluated at the temperature of the liquid phase.

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48. S. Murad and K.E. Gubbins, “Corresponding states correlation for thermal
conductivity of dense fluids,” Chemical Engineering Science, 32(5):499–505, 1977.

49. J.R. Cooper, “Revised Release on the IAPWS Formulation 2008 for the Viscosity
of Ordinary Water Substance”, The International Association for the Properties of
Water and Steam, Berlin, Germany, Sep. 2008.

50. K. Daucik, “Revised Release on the Pressure along the Melting and Sublimation
Curves of Ordinary Water Substance”, The International Association for the
Properties of Water and Steam, Plzen, Czech Republic, Sep. 2011.

51. J. Gabitto and M. Barrufet, “Experimental and theoretical determination of heavy

oil viscosity under reservoir conditions.”, Technical reports, Office of Fossile Energy.
USDOE Office of Fossil Energy, United States, 2002.

52. A. Missenard, “Conductivité thermique des liquides organiques d’une serie ou

d’un ‘groupe de liquides’,” Revue Générale de Thermique, vol. 101, no. 5, pp. 649–
660, 1970 (in French).

53. R.L. Rowley, G.L. White, and M. Chiu, “Ternary liquid mixture thermal
conductivities,” Chemical Engineering Science, vol. 43, no. 2, pp. 361–371, 1988.

54. R.L. Rowley, “A local composition model for multicomponent liquid mixture
thermal conductivities,” Chemical Engineering Science, vol. 37, no. 6, pp. 897–904,
1982.

692 | CHAPTER 9: THERMODYNAMICS

55. W.D. Niven, “The Scientific Papers of James Clerk Maxwell”, Cambridge
University Press, 1890.

56. J.C. Maxwell, “On the dynamical theory of gases,” Philosophical Transactions of
the Royal Society of London, vol. 157, pp. 49–88, 1867.

57. J. Stefan, “Uber das Gleichgewicht und die Bewegung, insbesondere die Diffusion
von Gasgemengen,” Sitzungsbrichte der Kaiserlichen Akademie der Wissenschaften
Wien, 2te Abteilung a, vol. 63, pp. 63–124, 1871.

58. R. Taylor and R. Krishna, “Multicomponent Mass Transfer,” Wiley-Interscience,

1993.

59. E.N. Fuller, P.D. Schettler and J.C. Giddings, “A new method for prediction of
binary gas-phase diffusion coefficients,” Industrial and Engineering Chemistry,
vol. 5, pp. 19–27, 1966.

60. E.N. Fuller, K. Ensley and J.C. Giddings, “Diffusion of halogenated hydrocarbons
in helium. The effect of structure on collision cross sections,” The Journal of Physical
Chemistry, vol. 73, no. 11, pp. 3679–3685, 1969.

61. C.R. Wilke and C.Y. Lee, “Estimation of diffusion coefficients for gases and
vapors,” Industrial and Engineering Chemistry, vol. 47, no. 6, pp. 1253–1257,
1955.

62. P.D. Neufeld, A.R. Janzen and R.A. Aziz, “Empirical equations to calculate 16 of
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the transport collision integrals  for the Lennard-Jones (12-6) potential,” The
Journal of Chemical Physics, vol. 57, pp. 1100–1102, 1972.

63. C.R. Wilke and P. Chang, “Correlation of diffusion coefficients in dilute

solutions,” AICHE Journal, vol. 1, no. 2, pp. 264–270, 1972.

64. W. Hayduk and H. Laudie, “Prediction of diffusion coefficients for nonelectrolytes

in dilute aqueous solutions,” AICHE Journal, vol. 20, no. 3, pp. 611–615, 1974.

65. H.A. Kooijman, “A modification of the Stokes-Einstein equation for diffusivities

in dilute binary mixture,” Industrial and Engineering Chemistry Research, vol. 41,
pp. 3326–3328, 2002.

66. M.T.Tyn and W.F Calus. Diffusion Coefficients in dilute binary mixtures. Journal
of Chemical and Engineering Data, vol. 20, no. 1, pp. 106–109, 1975.

67. W.Hayduk and B.S.Minhas, “Correlation for prediction of molecular diffusivities

in liquids,” Canadian Journal of Chemical Engineering, vol. 60, no. 2), pp. 295–
299, 1983.

THERMODYNAMIC MODELS AND THEORY | 693

 68. M.A. Siddiqi and K. Lucas, “Correlations for prediction of diffusion in liquids”,
The Canadian Journal of Chemical Engineering, vol. 64, pp. 839–843, 1986.

69. C. Erkey, J.B. Rodden and A. Akgerman, “A correlation for predicting diffusion
coefficients in alkanes”, The Canadian Journal of Chemical Engineering, vol. 68,
pp. 661–665, 1990.

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vol. 68, no. 3, pp. 441-451, 1964.

71. J.O. Hirschfelder, C.F. Curtiss and R.B. Bird, “The Molecular Theory of Gases
and Liquids”, Wiley-Interscience, 1964.

72. A. Vignes, “Diffusion in Binary Solutions,” Industrial and Engineering

Chemistry Fundamentals, vol. 5, pp. 189–199, 1966.

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ISBN: 0-13-553165-9.

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multicomponent liquid systems”, Industrial and Engineering Chemistry Research,
vol. 30, pp. 1217–1222, 1991.

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volume theory”, Chemical Engineering Research and Design, 75(6):590–602,
1997.

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694 | CHAPTER 9: THERMODYNAMICS

 10

Multiphysics Coupling Nodes

The Fuel Cell & Electrolyzer Module has multiphysics couplings available under
certain conditions.

When a predefined multiphysics interface is added from the Model Wizard or Add
Physics windows, it adds the constituent interfaces and the Multiphysics Couplings
node, which automatically includes one or more multiphysics couplings.

If the constituent physics interfaces are added one at a time, then it adds an empty
Multiphysics Couplings node. When you right-click this node, you can choose from
the available multiphysics couplings.

The Multiphysics Branch in the COMSOL Multiphysics Reference

Manual.

In this chapter, the following multiphysics couplings nodes are described:

• Electrochemical Heating • Potential Coupling

• Space Charge Density Coupling

695
 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.

696 | CHAPTER 10: MULTIPHYSICS COUPLING NODES

Reacting Flow, H2/O2 Gas Phase
The Reacting Flow, H2 Gas Phase and the Reacting Flow, O2 Gas Phase nodes couple a
fluid flow interface to a Hydrogen Fuel Cell (fc) or a Water Electrolyzer (we) interface.

The node sets up a two-way coupling so that the velocity field and pressure
distribution, calculated by the fluid flow interface, are used by the fc/we interface,
whereas the density and dynamic viscosity, calculated by the fc/we interface, are used
by the fluid flow interface.

| 697
698 | CHAPTER 10: MULTIPHYSICS COUPLING NODES
 11

Glossary

This Glossary of Terms contains application-specific terms used in the Fuel Cell &
Electrolyzer 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.

699
 Glossary of Terms
anode An electrode where oxidation occurs. Anodic charge transfer current densities
and overpotentials are positive by definition.

cathode An electrode where reduction occurs. Cathodic charge transfer current

densities and overpotentials are negative by definition.

cell voltage The difference in potential over an electrochemical cell.

charge transfer reaction A reaction during which charge is transferred from an

electron conducting phase (electrode) to an ion conducting phase (electrolyte).

charge transfer current density The current density at an electrolyte-electrode

interface associated with a charge transfer reaction.

concentrated electrolyte An electrolyte where the concentration of charged species is

so high that the interactions between the ions needs to be considered. See also diluted
electrolyte.

current collector A part of an electrochemical device with high electric conductivity

for conducting current out of the cell. See also current feeder.

current feeder A part of an electrochemical device with high electric conductivity for
conducting current into the cell. See also current collector.

diluted electrolyte An electrolyte where the charged species are diluted in a solvent so
that the interaction between the ions can be neglected. See also concentrated
electrolyte.

electric potential The potential in the electrode (electron conducting) phase, denoted
s (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.

700 | CHAPTER 11: GLOSSARY

electrolyte An ion conductor.

electrolyte potential The potential in the electrolyte (ionic) phase, denoted l (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 | 701

 COMSOL Multiphysics using the Transport of Diluted Species interface. The
Nernst-Planck equation is often combined with an electroneutrality condition, which
can be modeled in COMSOL Multiphysics using the Tertiary Current Distribution,
Nernst-Planck interface.

Nernst-Planck-Poisson equation In certain situations, for instance when striving to

resolve the electrochemical double layer at an electrode, and electrokinetic flow cannot
be assumed, the Nernst-Planck equation is combined with the Poisson’s equation for
describing the charge density.

overpotential A deviation from the equilibrium potential.

oxidation A charge transfer reaction where electrons are produced.

perfectly mixed electrolyte. An electrolyte where no concentration gradients are

present, for instance due to stirring. See also secondary current distribution.

primary current distribution The current distribution that is established when

overpotentials can be neglected — that is, when the current distribution is governed
by the electrolyte and electrode conductivities only. See also secondary current
distribution and tertiary current distribution.

Poisson’s equation An equation for relating the electric field to the space charge
density. Can be modeled in COMSOL using the Electrostatics interface.

pore electrolyte An electrolyte in the pores of a porous matrix. See porous electrode.

porous electrode A porous matrix containing both electron conducting and ion
conducting media.

potentiostat A device that monitors and controls the potential of an electrode versus
a reference electrode.

reduction A charge transfer reaction where electrons are consumed.

reference electrode An electrode used for reference when defining the potentials of
the electrodes in a cell. A good reference electrode is stable and does not vary in
potential. Typically no net reactions occur at a reference electrode surface, and the net
current density is zero.

702 | CHAPTER 11: 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 | 703

704 | CHAPTER 11: GLOSSARY
I n d e x
A absolute pressure 400, 454, 460, 479, 498 electrode, shell 152
activation overpotential 161, 168, 190 electrostatics 72
added mass force 570 Euler-Euler interface 496
adsorption 253, 261 free and porous media flow 440
amperometric sensing 187 mm interfaces 477
analyte 187 surface reactions 328
anodes 38 transport of concentrated species 273
anodic Tafel equation 171 transport of diluted species 228, 320
anodic transfer coefficient 162 boundary stress (node) 411
Application Libraries window 30 Brinkman equations 546
application library examples Brinkman equations interface 447
contact impedance 96 theory 546
convection and diffusion 232 bubble number density 552
Darcy’s law 419 Butler-Volmer and Tafel expressions
electric currents 88 tertiary current distribution 118
electrostatics 72 Butler-Volmer equation 47
free and porous media flow 440 electrode kinetics 168
laminar flow 398 secondary current distribution 161
migration in electric field 232 Butler–Volmer equation
mixture model, laminar flow 477 electroanalysis 192
storage model 426
C CAPE-OPEN compliant packages 603
transport of concentrated species 272
cathodes 38
transport of diluted species 226
cathodic charge transfer coefficient 162
Arrhenius parameters 300
cathodic Tafel equation 171
atmosphere/gauge (node) 436
CFL number
average linear velocity 543
settings 398, 449, 457, 476, 495
B Basset force 570 change cross-section (node) 84
boundary current source (node) 93, 155 change thickness (out-of-plane) (node)
boundary electrolyte potential 143, 209, 84
324 charge conservation (node) 74
boundary nodes charge conservation, piezoelectric
Brinkman equations 449 (node) 85
bubbly flow 458 charge relaxation theory 101
Darcy’s law interface 419 charge transfer reaction 161
electric currents 88 charge transfer reactions 136
electrochemistry interfaces 128 checklist, for modeling 59

INDEX| 705
 chemical equilibrium 298 320
chronoamperometry 187 electrostatics 72
common settings 29 Euler-Euler interface 496
conduction loss (time-harmonic) (node) free and porous media flow 440
76 mm interfaces 477
contact impedance (node) 95 transport of concentrated species 273
continuity equation, multiphase flow 557 transport of diluted species 228
convection 352 double layer capacitance (node) 142
convective terms, diluted species 344 drag force 570
coulometry 187 drag law, Hadamard-Rybczynski 563
creeping flow (spf) interface 393 Dusty gas model 269
critical point 619
E edge electrode (node) 114
current (node) 323
edge nodes
current density (node) 323
Darcy’s law interface 419
current source (node) 154
electric currents 88
current sources, theory 103
electrochemistry interfaces 128
cyclic voltammetry 187
electrode, shell 152
D Darcy velocity 352, 431 electrostatics 72
Darcy’s law interface 417 surface reactions 328
theory 540 electric currents interface 86
Debye length 42 theory 105
dense flows 571 electric displacement field (node) 79
diffusion models 268 electric fields theory 101
dispersed liquid droplets 568 electric insulation (node)
dispersed phase boundary conditions electrode, shell 155
560 electric potential (node) 78
dispersed phase number density 559 electrode, shell 156
dispersed phase particles 566 electric reference potential (node) 149
dispersed solid particles 569 electroanalysis interface 157
distributed impedance (node) 94 theory 187
documentation 29 electroanalysis, definition 187
domain nodes electrochemical cells 38
Brinkman equations 449 electrochemical impedance spectrosco-
bubbly flow 458 py (EIS) 187
Darcy’s law 419 electrochemical sensing 187
electric currents 88 electrode 160
electrochemistry interfaces 128 electrode (node)
electrophoretic transport interface electrochemistry 130

706 | I N D E X
 electrode, shell 153 electrolyte points current source (node)
electrode current (node) 146, 210 116
electrode current density (node) 146, electrolyte potential 163
211 electrolyte potential (node) 143, 209
electrode current source (node) 130 electrolyte symmetry axis current
electrode line current source (node) 115 source (node) 116
electrode points current source (node) electrolyte-electrode domain interface
116 (node) 142
electrode potential (node) 148 electrolytes 37
electrode power (node) 147, 211 electromagnetic heat source (multiphys-
electrode reaction (node) ics coupling) 696
electrochemistry 136 electroneutrality 42
electrode surface (node) 133 electrophoretic transport interface 314
electrode symmetry axis current source electrostatics interface 70
(node) 116 theory 101
electrode, shell interface 151 elevation 427
theory 185 emailing COMSOL 30
electrode-electrolyte boundary interface EnthalpyF 619
(node) EntropyF 619
current distribution 145 Eötvös number 553
electrode-electrolyte interface coupling equation of continuity 101
(node) equilibrium potential 161
free and porous media flow 428, 444 Equilibrium Reaction
transport of diluted species 246, 281 theory for 342
electrode-electrolyte interfaces 38 equilibrium reaction (node) 243, 291
electrodes 37 equilibrium reaction group (node) 309
electrolysis 37 Ergun packed bed expression 571
electrolyte 160 Ettehadieh solid pressure model 575
electrolyte (node) Euler-Euler equations 575
primary and secondary current distri- bubbly flow 549
bution 111 Euler-Euler model, laminar flow (ee) in-
tertiary current distribution 122 terface 493
electrolyte current (node) 143 theory 566
electrolyte current density (node) 144, external short circuit (node) 148
210 external surface charge accumulation
electrolyte current source (node) 131 (node) 79
electrolyte line current source (node) external thermodynamic packages 603
115
F faradaic current 51

INDEX| 707
 Faraday’s constant 162 gas diffusion 364
Faraday’s law 348 gas reacting fluids 294, 304
Faraday’s laws of electrolysis 191 Gauss’ law and charge relaxation theory
Fick diffusion laws 189 101
Fick equations and diffusivities 364 Gauss’ law equation 103
Fick’s law approximation diffusion 370 general stress (boundary stress condi-
Fick’s law diffusion model 270 tion) 411
flash calculation Gibbs free energy 302
retrograde solution type 619 Gidaspow and Ettehadieh solid pressure
solution type 619–620 model 575
flash calculations 617 Gidaspow model 571
flow continuity (node) 413, 471, 508 Gidaspow solid pressure model 575
flow rate in SCCMs 407 gravity 416
fluid and matrix properties (node) gravity (node)
Brinkman equations 450 bf interfaces 463
Darcy’s law 421 ee interfaces 502
fluid flow mm interfaces 483
Brinkman equations theory 546 ground (node) 77, 155
fluid properties (node) 441
H H2 inlet (node)
bf interfaces 459
hydrogen fuel cell 212
fluid-solid mixtures 568
Hadamard-Rybczynski drag law 563
flux (node) 263, 325
Haider-Levenspiel slip model 563
transport of concentrated species 287
harmonic perturbation (node) 147
transport of diluted species 263, 325
Henry’s law 462
flux discontinuity (node) 238
heterogeneous rate constant 192
Darcy’s law 432
hydraulic head (node) 435
transport of concentrated species 290
Hygroscopic Swelling 256
transport of diluted species 238
I implementing, Euler-Euler equations 575
fracture flow (node) 438
inflow (node) 235, 326
free and porous matrix properties
transport of concentrated species 288
(node) 442
initial values (node)
free and porous media flow interface 439
bf interfaces 463
theory 545
Brinkman equations 453
Freundlich exponent 358
corroding electrode surface node 148
fully developed flow 407
Darcy’s law 424
G galvanic cells 37
depositing electrode surface node 148
gas boundary conditions 472
ee interface 501
gas constant 390
electric currents 92

708 | I N D E X
 electrode, shell 154 lift force 570
electrostatics 76 line charge (node) 81
free and porous media flow 444 line charge (on axis) (node) 82
mm interfaces 483 line charge (out-of-plane) (node) 82
primary and secondary current distri- line current source (node) 97
bution 111 line current source (on axis) (node) 98
single-phase, laminar flow 401 line mass source (node)
spf interfaces 401 fluid flow 415
surface reactions 330 species transport 240
tertiary current distribution 125 line source
transport of concentrated species 285 species transport 346
transport of diluted species 233 liquid reacting fluids 294, 304
inlet (node) 404 local
bf interfaces 466 CFL number 398, 449, 457, 476, 495
ee interface 505
M mass action law, laminar flow 389
mm interfaces 487
mass based concentrations (node) 233
single-phase flow 404
mass fraction (node) 286
insulation (node) 132, 209, 324
mass source (node)
interior wall (node)
Brinkman equations 452
bf interfaces 470
Darcy’s law 424
ee interface 507
mass transfer (node)
mm interfaces 491
bf interfaces 462
internet resources 29
ee interfaces 502
interphase momentum transfer 570
mm interfaces 482
intrinsic volume averages 546
mass transport 363
irreversible reaction 298
Maxwell-Stefan diffusion model 269
K knowledge base, COMSOL 31 Maxwell-Stefan diffusivity matrix 367
Knudsen diffusion 269 mixture continuity (node) 492
Krieger type model 569 mixture model, laminar flow (mm) inter-
Krieger type viscosity model 481 face 473
mixture properties (node) 478
L laminar bubbly flow (bf) interface 455
mixture viscosity 480
theory 549
mixture-averaged diffusion model 270,
laminar flow interface 394
368
laminar mixture model (mm) interface
modeling checklist 59
theory 556
momentum balance equations 567
Langmuir constant 358
monolayer adsorption 380
leaking wall, wall boundary condition
MPH-files 30
402, 445

INDEX| 709
 multicomponent diffusion 366 transport of concentrated species 289
multiphase flash calculations 604 transport of diluted species 236
multiphase flow theory 549, 556 outlet (node) 408
multiphysics couplings bf interfaces 467
electromagnetic heat source (node) hydrogen fuel cell 212
696 mm interfaces 488
single-phase flow 408
N Nernst equation 192
spf interfaces 408
Nernst-Einstein relation 231, 248, 252,
overpotential 46, 161
348
Nernst-Planck equations 41, 158 P pair contact impedance (node) 95
Nernst-Planck-Poisson equations 42 pair nodes
Nernst-Planck-Poisson Equations inter- Brinkman equations 449
face 312 Darcy’s law interface 419
no flow (node) 432 electric currents 88
no flux (node) 235 electrochemistry interfaces 128
hydrogen fuel cell 211 electrode, shell 152
transport of concentrated species 289 electrophoretic transport interface
no slip, wall boundary condition 402, 445 320
no viscous stress (open boundary) 411 electrostatics 72
nodes, common settings 29 Euler-Euler interface 496
nonconservative formulations 344 free and porous media flow 440
non-faradaic reactions (node) 149 surface reactions 328
normal current density (node) 155 transport of concentrated species 273
normal stress, normal flow (boundary transport of diluted species 228
stress condition) 412 partially saturated porous media (node)
250
O O2 inlet (node)
periodic condition (node) 113
hydrogen fuel cell 212
transport of diluted species 240
Ohm’s law 108, 160, 349
periodic flow condition (node) 412, 469,
Ohm’s law and charge relaxation theory
490
101
permeability models 423
ohmic drop 188
persistence
open boundary (node)
of thermodynamic packages 607
single-phase flow 410
pervious layer (node) 436
spf interfaces 410
phase properties (node) 497
transport of concentrated species 290
physics interfaces, common settings 29
transport of diluted species 242
point charge (node) 83
outflow (node)
point charge (on axis) (node) 83
electrophoretic transport 326

710 | I N D E X
point current source (node) 98 potentiostat 195
point current source (on axis) (node) 99 pressure (node) 428, 431, 433
point mass source (node) pressure head (node) 435
fluid flow 414 pressure point constraint (node) 414
species transport 241 primary current distribution 39
point nodes primary current distribution interface
Brinkman equations 449 108
Darcy’s law interface 419 theory 158
electric currents 88 pseudo time step 387
electrochemistry interfaces 128 pseudo time stepping
electrode, shell 152 settings 398, 449, 457, 476, 495
electrostatics 72
R reacting fluids, gases and liquids 294, 304
Euler-Euler interface 496
Reacting Volume 234, 266
free and porous media flow 440
reaction (node) 297
surface reactions 328
reaction coefficients (node) 245
point source
reaction thermodynamics (node) 310
species transport 345
reactions (node)
poroelastic storage (node)
surface reactions 330
Darcy’s law 426
tertiary current distribution 125
porous electrode (node) 112, 123
transport of concentrated species 284
porous electrode coupling (node) 245
transport of diluted species 233
free and porous media flow 427, 444
reference electrode (node) 149
porous electrode reaction (node) 131
resistive film 166
porous electrodes 111, 161
retardation factor 358
porous matrix double layer capacitance
Reuss average 425
(node) 132
reversible reaction 298
porous media and subsurface flow
reversible reaction group (node) 307
Brinkman equations interface 447
Reynolds number
Darcy’s law interface 417
slip velocity models 563
free and porous media flow interface
S SCCM, flow rate in 407
439
Schiller-Naumann slip model 563
theory, Brinkman equations 546
Schmidt number 562, 578, 580
theory, free and porous media flow
secondary current distribution 39
545
secondary current distribution interface
porous media transport properties
108
(node) 246, 250
theory 158
potential (node) 324
sector symmetry (node) 96
potentiometry 187
SEMI standard E12-0303 406

INDEX| 711
 separator (node) surface concentration (node) 331
current distribution 124 surface equilibrium reaction (node) 244,
single-phase flow interface 292
laminar flow 394 surface properties (node) 329
sliding wall 403, 487, 504 surface reactions interface 327
slip model theory 379
Hadamard-Rybczynski 563 symmetry (node) 410
Schiller-Naumann 563 bf interfaces 469
slip model theory 552 Darcy’s law 432
Haider-Levenspiel 563 electrochemistry 132
Reynolds number 563 mm interfaces 490
slip, wall boundary condition 402, 445 spf interfaces 410
solid pressure and particle interaction transport of concentrated species 289
574 transport of diluted species 238
Soret effect 371
T Tafel equation 171
space charge density (node) 77
Tafel law 47
species (node) 302
technical support, COMSOL 30
species activity (node) 311
tertiary current distribution 39
species group (node) 310
tertiary current distribution interface
species source (node) 324
theory 158
species thermodynamics (node) 311
tertiary current distribution,
standard cubic centimeters per minute
Nernst-Planck interface 118
407
theory
standard flow rate 407
bf interfaces 549
standard settings 29
Brinkman equations 546
stoichiometric coefficients 302
Darcy’s law 540
Stokes equations 393
electric currents interface 105
Stokes flow 393
electric fields 101
storage model (node)
electroanalysis interface 187
Darcy’s law 425
electrode, shell interface 185
stratified porous media 356
electrostatics interface 101
superficial volume average, porous me-
Euler-Euler model, laminar flow 566
dia 546
free and porous media flow 545
superficial volume averages, porous me-
mm interfaces 556
dia 352
primary current distribution interface
supporting electrolyte 187
158
Supporting Electrolytes 348
secondary current distribution inter-
surface charge density (node) 78
face 158

712 | I N D E X
 surface reactions 379 bubbly flow 549
tertiary current distribution interface
U Ungarish 565
158
V viscous drag, coefficient 553
transport of concentrated species in-
voltammetry, cyclic 187
terface 363
volume averages 546
transport of diluted species in porous
volume force (node) 401, 452
media interface 341
free and porous media flow 443
transport of diluted species interface
spf interfaces 401
340
thermal diffusion 371 W wall (node)
thermodynamics package 603 bf interfaces 464
adding 604 ee interface 503
thickness free and porous media flow 445
fracture 257 mm interfaces 484
out-of-plane 434 single-phase flow 402
thin diffusion barrier (node) 242 websites, COMSOL 31
Thin Impermeable Barrier 242 Wen and Yu fluidized state expression
thin low permittivity gap (node) 81 571
tortuosity factors 354
Z zero charge (node) 77
traction boundary conditions 411
transport mechanisms 274, 278, 281
transport of concentrated species inter-
face 267
theory 363
transport of diluted species in porous
media interface 226
theory 341
transport of diluted species interface
222, 258
theory 340
turbulent bubbly flow (bf) interface
theory 549
turbulent mixing (node)
transport of concentrated species 282
transport of diluted species 232
turbulent mixture model (mm) interface
theory 556
two-fluid Euler-Euler model

INDEX| 713
714 | I N D E X