Battery Design Module

User’s Guide
Battery Design Module User’s Guide
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Part number: CM021501

C o n t e n t s

Chapter 1: Introduction

About the Battery Design Module 26

What Can the Battery Design Module Do? . . . . . . . . . . . . . 26
Battery Design Module Physics Interface Guide . . . . . . . . . . . 27
Common Physics Interface and Feature Settings and Nodes . . . . . . 31
Where Do I Access the Documentation and Application Libraries? . . . . 31

Overview of the User’s Guide 34

Chapter 2: Modeling with Electrochemistry

Introduction to Electrochemistry Modeling 38

What Is Electrochemistry? . . . . . . . . . . . . . . . . . . . 38
Electrochemical Applications . . . . . . . . . . . . . . . . . . 39
Fundamentals of Electrochemistry Modeling . . . . . . . . . . . . 39
Current Distribution Cases and Choosing the Right Interface to
Model an Electrochemical Cell . . . . . . . . . . . . . . . . 41
Understanding the Different Approximations for Conservation of
Charge in Electrolytes . . . . . . . . . . . . . . . . . . . 42
Modeling Electrochemical Reactions . . . . . . . . . . . . . . . 46
Double Layer Capacitance . . . . . . . . . . . . . . . . . . . 53
Porous Electrodes . . . . . . . . . . . . . . . . . . . . . . 54
Boundary Conditions for Running and Controlling Electrochemical
Cells . . . . . . . . . . . . . . . . . . . . . . . . . . 55
Battery Modeling . . . . . . . . . . . . . . . . . . . . . . . 56
Modeling Cyclic Voltammetry . . . . . . . . . . . . . . . . . . 57
Common Simplifications When Modeling Electrochemical Cells . . . . . 58
Before You Start Building Your Model . . . . . . . . . . . . . . . 60
Meshing Advice . . . . . . . . . . . . . . . . . . . . . . . 61
Solving Electrochemical Models . . . . . . . . . . . . . . . . . 62
Postprocessing Your Solution . . . . . . . . . . . . . . . . . . 66

CONTENTS |3
 Connecting to Electrical Circuits 69
About Connecting Electrical Circuits to Physics Interfaces . . . . . . . 69
Connecting Electrical Circuits Using Predefined Couplings . . . . . . . 70
Connecting Electrical Circuits by User-Defined Couplings . . . . . . . 70
Solving . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
Postprocessing. . . . . . . . . . . . . . . . . . . . . . . . 72
References . . . . . . . . . . . . . . . . . . . . . . . . . 72

SPICE Import and Export 73

SPICE Import . . . . . . . . . . . . . . . . . . . . . . . . 73
SPICE Export . . . . . . . . . . . . . . . . . . . . . . . . 74
Reference . . . . . . . . . . . . . . . . . . . . . . . . . 75

Chapter 3: Battery Interfaces

The Lithium-Ion Battery Interface 79

About the Domain, Boundary, Edge, Point, and Pair Nodes for the
Lithium-Ion Battery Interface . . . . . . . . . . . . . . . . . 83
Initial Values . . . . . . . . . . . . . . . . . . . . . . . . 83
Electrode Reaction . . . . . . . . . . . . . . . . . . . . . . 84

Lithium-Ion Battery, Deformed Geometry Model Wizard Entry

85
Modeling Deformation of an Electrode Surface . . . . . . . . . . . 86
Tangential Velocities at the Intersection Between a Depositing and a
Nondepositing Boundary . . . . . . . . . . . . . . . . . . 86

The Battery with Binary Electrolyte Interface 89

Domain, Boundary, Edge, Point, and Pair Nodes for the Battery
with Binary Electrolyte Interface. . . . . . . . . . . . . . . . 93
Initial Values . . . . . . . . . . . . . . . . . . . . . . . . 93
Porous Matrix Adsorption/Desorption Reaction . . . . . . . . . . . 93

The Lead–Acid Battery Interface 95

Domain, Boundary, Edge, Point, and Pair Nodes for the Lead–Acid
Battery Interface. . . . . . . . . . . . . . . . . . . . . . 97

4 | CONTENTS
Reservoir. . . . . . . . . . . . . . . . . . . . . . . . . . 98
Initial Values . . . . . . . . . . . . . . . . . . . . . . . . 98
Negative Porous Electrode . . . . . . . . . . . . . . . . . . . 99
Positive Porous Electrode . . . . . . . . . . . . . . . . . . . 99
Separator. . . . . . . . . . . . . . . . . . . . . . . . . 100

The Single Particle Battery Interface 101

Model Tree Nodes for the Single Particle Battery Interface . . . . . . 105
Electrolyte and Separator . . . . . . . . . . . . . . . . . . 105
Positive Electrode . . . . . . . . . . . . . . . . . . . . . 106
Negative Electrode . . . . . . . . . . . . . . . . . . . . . 106
Lithium Insertion Reaction . . . . . . . . . . . . . . . . . . 106

The Lumped Battery Interface 108

Model Tree Nodes for the Lumped Battery Interface . . . . . . . . 111
Cell Equilibrium Potential. . . . . . . . . . . . . . . . . . . 111
Voltage Losses . . . . . . . . . . . . . . . . . . . . . . . 111
Capacity Loss . . . . . . . . . . . . . . . . . . . . . . . 112
Short Circuit . . . . . . . . . . . . . . . . . . . . . . . 113

The Battery Equivalent Circuit Model Wizard Entry 114

The Battery Pack Interface 115

Model Tree Nodes for the Battery Pack Interface . . . . . . . . . 116
Batteries . . . . . . . . . . . . . . . . . . . . . . . . . 117
Thermal Event . . . . . . . . . . . . . . . . . . . . . . . 117
Current Conductors . . . . . . . . . . . . . . . . . . . . 118
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 118
Negative Connectors . . . . . . . . . . . . . . . . . . . . 119
Positive Connectors . . . . . . . . . . . . . . . . . . . . 119

Shared Nodes for Battery Interfaces 120

Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . 121
Separator. . . . . . . . . . . . . . . . . . . . . . . . . 122
Porous Electrode. . . . . . . . . . . . . . . . . . . . . . 122
Particle Intercalation . . . . . . . . . . . . . . . . . . . . 124
Porous Electrode Reaction . . . . . . . . . . . . . . . . . . 127
Reaction Source . . . . . . . . . . . . . . . . . . . . . . 128

CONTENTS |5
 Additional Porous Electrode Material . . . . . . . . . . . . . . 129
Porous Conductive Binder . . . . . . . . . . . . . . . . . . 129
Concentration . . . . . . . . . . . . . . . . . . . . . . . 131
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 131
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
Initial Cell Charge Distribution . . . . . . . . . . . . . . . . 131
Negative Electrode Selection . . . . . . . . . . . . . . . . . 133
Positive Electrode Selection . . . . . . . . . . . . . . . . . . 133

Theory for the Lithium-Ion Battery Interface 134

References . . . . . . . . . . . . . . . . . . . . . . . . 144

Theory for the Battery with Binary Electrolyte Interface 145

Theory for the Lead–Acid Battery Interface 153

The Electrode Reactions Equations . . . . . . . . . . . . . . . 153
Electrode Kinetics and Active Available Surface Areas . . . . . . . . 154
Electrode Charge Transport Equations . . . . . . . . . . . . . 154
Electrolyte Transport Equations . . . . . . . . . . . . . . . . 155

Theory for the Single Particle Battery Interface 159

Theory for the Lumped Battery Interface 166

Theory for the Battery Pack Interface 173

Chapter 4: Electrochemistry Interfaces

The Primary and Secondary Current Distribution Interfaces 178

The Primary Current Distribution and Secondary Current Distribution
Interfaces . . . . . . . . . . . . . . . . . . . . . . . 178
Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . 181
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 182
Porous Electrode. . . . . . . . . . . . . . . . . . . . . . 182
Periodic Condition . . . . . . . . . . . . . . . . . . . . . 184
Thin Electrolyte Layer . . . . . . . . . . . . . . . . . . . . 184

6 | CONTENTS
Edge Electrode. . . . . . . . . . . . . . . . . . . . . . . 185
Electrode Line Current Source . . . . . . . . . . . . . . . . 186
Electrolyte Line Current Source . . . . . . . . . . . . . . . . 186
Electrode Symmetry Axis Current Source . . . . . . . . . . . . 186
Electrolyte Symmetry Axis Current Source . . . . . . . . . . . . 187
Electrode Point Current Source . . . . . . . . . . . . . . . . 187
Electrolyte Point Current Source. . . . . . . . . . . . . . . . 187
Electrode Current . . . . . . . . . . . . . . . . . . . . . 187

The Tertiary Current Distribution, Nernst-Planck Interface 188

The Tertiary Current Distribution, Nernst–Planck Interface . . . . . 188
Electrolyte . . . . . . . . . . . . . . . . . . . . . . . . 193
Porous Electrode. . . . . . . . . . . . . . . . . . . . . . 194
Separator. . . . . . . . . . . . . . . . . . . . . . . . . 195
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 195
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 195
Ion Exchange Membrane . . . . . . . . . . . . . . . . . . . 196
Ion Exchange Membrane Boundary . . . . . . . . . . . . . . . 196
Thin Electrolyte Layer . . . . . . . . . . . . . . . . . . . . 197

Shared Physics Features in the Current Distribution Interfaces

198
Domain, Boundary, Pair, Edge, and Point Nodes for the
Electrochemistry Interfaces . . . . . . . . . . . . . . . . 198
Electrode. . . . . . . . . . . . . . . . . . . . . . . . . 200
Highly Conductive Porous Electrode . . . . . . . . . . . . . . 200
Electrode Current Source . . . . . . . . . . . . . . . . . . 200
Electrolyte Current Source . . . . . . . . . . . . . . . . . . 201
Porous Electrode Reaction . . . . . . . . . . . . . . . . . . 201
Porous Matrix Double Layer Capacitance . . . . . . . . . . . . 202
Insulation . . . . . . . . . . . . . . . . . . . . . . . . . 202
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 202
Electrode Surface. . . . . . . . . . . . . . . . . . . . . . 203
Electrode Reaction . . . . . . . . . . . . . . . . . . . . . 207
Double Layer Capacitance . . . . . . . . . . . . . . . . . . 212
Perforated Electrode Surface . . . . . . . . . . . . . . . . . 213
Internal Electrode Surface . . . . . . . . . . . . . . . . . . 213
Electrolyte Potential . . . . . . . . . . . . . . . . . . . . 214

CONTENTS |7
 Electrolyte Current . . . . . . . . . . . . . . . . . . . . . 214
Electrolyte Current Density. . . . . . . . . . . . . . . . . . 215
Thin Electrode Layer . . . . . . . . . . . . . . . . . . . . 215
Electrode-Electrolyte Boundary Interface. . . . . . . . . . . . . 216
Electric Ground . . . . . . . . . . . . . . . . . . . . . . 216
Electric Potential . . . . . . . . . . . . . . . . . . . . . . 217
Electrode Current Density . . . . . . . . . . . . . . . . . . 217
Electrode Current . . . . . . . . . . . . . . . . . . . . . 217
Electrode Power . . . . . . . . . . . . . . . . . . . . . . 218
Harmonic Perturbation . . . . . . . . . . . . . . . . . . . 218
Electrode Potential . . . . . . . . . . . . . . . . . . . . . 219
External Short . . . . . . . . . . . . . . . . . . . . . . . 219
Initial Values for Adsorbing-Desorbing Species. . . . . . . . . . . 220
Initial Values for Dissolving-Depositing Species . . . . . . . . . . 220
Non-Faradaic Reactions . . . . . . . . . . . . . . . . . . . 220
Reference Electrode . . . . . . . . . . . . . . . . . . . . 220
Electric Reference Potential . . . . . . . . . . . . . . . . . . 221
Charge-Discharge Cycling . . . . . . . . . . . . . . . . . . 221
Circuit Terminal . . . . . . . . . . . . . . . . . . . . . . 222

The Electrode, Shell Interface 223

Boundary, Edge, Point, and Pair Nodes for the Electrode, Shell
Interface. . . . . . . . . . . . . . . . . . . . . . . . 224
Electrode . . . . . . . . . . . . . . . . . . . . . . . . . 225
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 226
External Current Density . . . . . . . . . . . . . . . . . . 226
Current Source . . . . . . . . . . . . . . . . . . . . . . 226
Normal Current Density . . . . . . . . . . . . . . . . . . . 227
Electric Insulation . . . . . . . . . . . . . . . . . . . . . 227
Boundary Current Source . . . . . . . . . . . . . . . . . . 227
Ground . . . . . . . . . . . . . . . . . . . . . . . . . 227
Electric Potential . . . . . . . . . . . . . . . . . . . . . . 228

The Electroanalysis Model Wizard Entry 229

Theory for the Current Distribution Interfaces 230

The Nernst–Planck Equations . . . . . . . . . . . . . . . . . 230
Domain Equations for Primary and Secondary Current Distributions . . 231

8 | CONTENTS
Electrochemical Reactions and the Difference Between a Primary and
a Secondary Current Distribution . . . . . . . . . . . . . . 232
Domain Equations for Tertiary Current Distributions Using the
Nernst–Planck Equations and Electroneutrality . . . . . . . . . 235
Mass Fluxes and Sources Due to Electrochemical Reactions . . . . . 236
Deposition-Dissolution Rates, Growth Velocities, and Thicknesses on
an Electrode Surface . . . . . . . . . . . . . . . . . . . 237
Stoichiometric Coefficients for Double Layer Capacitive Charging . . . 238
Film Resistance . . . . . . . . . . . . . . . . . . . . . . 239
Equilibrium Potentials and the Nernst Equation . . . . . . . . . . 239
Electrode Kinetics Expressions . . . . . . . . . . . . . . . . 240
Theory for Specific Current Distribution Feature Nodes . . . . . . . 245
Reference . . . . . . . . . . . . . . . . . . . . . . . . 252

Theory for Electrochemical Heat Sources 253

Joule Heating Due to Charge Transport . . . . . . . . . . . . . 254
Heating Due to Electrochemical Reactions . . . . . . . . . . . . 254
Heating Due to Heat of Mixing . . . . . . . . . . . . . . . . 255
Heat of Mixing in Intercalating Electrodes . . . . . . . . . . . . 256
Total Overpotential Calculation for Concentration Dependent Kinetics . 257
References . . . . . . . . . . . . . . . . . . . . . . . . 258

Theory for the Electrode, Shell Interface 259

Governing Equations . . . . . . . . . . . . . . . . . . . . 259
Coupling to Other Physics Interfaces . . . . . . . . . . . . . . 259

Theory for Electroanalysis 261

Electroanalytical Methods . . . . . . . . . . . . . . . . . . 261
Supporting Electrolyte . . . . . . . . . . . . . . . . . . . . 261
Domain Equations for the Electroanalysis Case . . . . . . . . . . 262
Electrode Boundary Conditions in the Electroanalysis Model . . . . . 264
The Electroanalytical Butler-Volmer Equation . . . . . . . . . . . 266
Counter Electrodes and Overall Charge Balance . . . . . . . . . . 267

Electrode Potentials and Reference Electrodes 268

Reference Electrodes . . . . . . . . . . . . . . . . . . . . 268
Boundary Conditions Using Reference Electrode Potentials. . . . . . 269
Nodes for Handling Electrode Potentials and Reference Electrodes. . . 269

CONTENTS |9
 Chapter 5: AC/DC Interfaces

The Electrostatics Interface 272

Domain, Boundary, Edge, Point, and Pair Nodes for the
Electrostatics Interface . . . . . . . . . . . . . . . . . . 274
Charge Conservation . . . . . . . . . . . . . . . . . . . . 276
Conduction Loss (Time-Harmonic) . . . . . . . . . . . . . . . 277
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 278
Space Charge Density . . . . . . . . . . . . . . . . . . . . 279
Zero Charge . . . . . . . . . . . . . . . . . . . . . . . 279
Ground . . . . . . . . . . . . . . . . . . . . . . . . . 279
Electric Potential . . . . . . . . . . . . . . . . . . . . . . 280
Surface Charge Density . . . . . . . . . . . . . . . . . . . 280
External Surface Charge Accumulation . . . . . . . . . . . . . 281
Symmetry Plane (for Electric Field) . . . . . . . . . . . . . . . 281
Electric Displacement Field . . . . . . . . . . . . . . . . . . 282
Periodic Condition . . . . . . . . . . . . . . . . . . . . . 282
Thin Low Permittivity Gap . . . . . . . . . . . . . . . . . . 284
Line Charge . . . . . . . . . . . . . . . . . . . . . . . . 284
Line Charge (on Axis) . . . . . . . . . . . . . . . . . . . . 285
Line Charge (Out-of-Plane) . . . . . . . . . . . . . . . . . . 285
Point Charge . . . . . . . . . . . . . . . . . . . . . . . 286
Point Charge (on Axis) . . . . . . . . . . . . . . . . . . . 287
Change Cross Section . . . . . . . . . . . . . . . . . . . . 287
Change Thickness (Out-of-Plane). . . . . . . . . . . . . . . . 288
Charge Conservation, Piezoelectric . . . . . . . . . . . . . . . 288

The Electric Currents Interface 290

Domain, Boundary, Edge, Point, and Pair Nodes for the Electric
Currents Interface . . . . . . . . . . . . . . . . . . . . 292
Current Conservation . . . . . . . . . . . . . . . . . . . . 294
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 296
External Current Density . . . . . . . . . . . . . . . . . . 296
Current Source . . . . . . . . . . . . . . . . . . . . . . 297
Electric Insulation . . . . . . . . . . . . . . . . . . . . . 297
Boundary Current Source . . . . . . . . . . . . . . . . . . 297
Normal Current Density . . . . . . . . . . . . . . . . . . . 298

10 | C O N T E N T S
Distributed Impedance. . . . . . . . . . . . . . . . . . . . 298
Contact Impedance . . . . . . . . . . . . . . . . . . . . . 299
Sector Symmetry . . . . . . . . . . . . . . . . . . . . . . 300
Line Current Source . . . . . . . . . . . . . . . . . . . . 301
Line Current Source (on Axis). . . . . . . . . . . . . . . . . 302
Point Current Source . . . . . . . . . . . . . . . . . . . . 302
Point Current Source (on Axis) . . . . . . . . . . . . . . . . 303
Piezoresistive Material . . . . . . . . . . . . . . . . . . . . 303

The Electrical Circuit Interface 305

Ground Node . . . . . . . . . . . . . . . . . . . . . . . 306
Voltmeter . . . . . . . . . . . . . . . . . . . . . . . . 307
Ampère Meter. . . . . . . . . . . . . . . . . . . . . . . 307
Resistor . . . . . . . . . . . . . . . . . . . . . . . . . 307
Capacitor. . . . . . . . . . . . . . . . . . . . . . . . . 308
Inductor . . . . . . . . . . . . . . . . . . . . . . . . . 308
Voltage Source . . . . . . . . . . . . . . . . . . . . . . 308
Current Source . . . . . . . . . . . . . . . . . . . . . . 309
Voltage-Controlled Voltage Source . . . . . . . . . . . . . . . 310
Voltage-Controlled Current Source. . . . . . . . . . . . . . . 311
Current-Controlled Voltage Source. . . . . . . . . . . . . . . 311
Current-Controlled Current Source . . . . . . . . . . . . . . 311
Switch . . . . . . . . . . . . . . . . . . . . . . . . . . 312
Subcircuit Definition . . . . . . . . . . . . . . . . . . . . 313
Subcircuit Instance . . . . . . . . . . . . . . . . . . . . . 313
NPN BJT and PNP BJT. . . . . . . . . . . . . . . . . . . . 314
n-Channel MOSFET and p-Channel MOSFET . . . . . . . . . . . 314
Mutual Inductance . . . . . . . . . . . . . . . . . . . . . 315
Transformer . . . . . . . . . . . . . . . . . . . . . . . 315
Battery Open Circuit Voltage . . . . . . . . . . . . . . . . . 316
Resistor-Capacitor Couple . . . . . . . . . . . . . . . . . . 316
Diode . . . . . . . . . . . . . . . . . . . . . . . . . . 317
External I vs. U . . . . . . . . . . . . . . . . . . . . . . 317
External U vs. I . . . . . . . . . . . . . . . . . . . . . . 318
External I-Terminal . . . . . . . . . . . . . . . . . . . . . 319
SPICE Circuit Import . . . . . . . . . . . . . . . . . . . . 320
SPICE Circuit Export . . . . . . . . . . . . . . . . . . . . 320

CONTENTS | 11
 Theory for the Electrostatics Interface 322
Charge Relaxation Theory . . . . . . . . . . . . . . . . . . 322
Electrostatics Equations . . . . . . . . . . . . . . . . . . . 324
The Electrostatics Interface in Time Dependent or Frequency
Domain Studies . . . . . . . . . . . . . . . . . . . . . 325

Theory for the Electric Currents Interface 326

Electric Currents Equations in Steady State . . . . . . . . . . . . 326

Theory for the Electrical Circuit Interface 328

Electric Circuit Modeling and the Semiconductor Device Models. . . . 328
Bipolar Transistors . . . . . . . . . . . . . . . . . . . . . 329
MOSFET Transistors . . . . . . . . . . . . . . . . . . . . 332
Diode . . . . . . . . . . . . . . . . . . . . . . . . . . 335
Reference for the Electrical Circuit Interface . . . . . . . . . . . 337

Chapter 6: Chemical Species Transport Interfaces

The Transport of Diluted Species Interface 340

The Transport of Diluted Species in Porous Media Interface . . . . . 344
Domain, Boundary, and Pair Nodes for the Transport of Diluted
Species Interface. . . . . . . . . . . . . . . . . . . . . 345
Prescribing Conditions on Fluid-Solid Interfaces . . . . . . . . . . 348
Species Properties . . . . . . . . . . . . . . . . . . . . . 348
Transport Properties . . . . . . . . . . . . . . . . . . . . 349
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 351
Mass-Based Concentrations . . . . . . . . . . . . . . . . . . 351
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 352
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 353
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 354
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 354
Concentration . . . . . . . . . . . . . . . . . . . . . . . 355
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 357
Flux Discontinuity . . . . . . . . . . . . . . . . . . . . . 357
Partition Condition . . . . . . . . . . . . . . . . . . . . . 357

12 | C O N T E N T S
Periodic Condition . . . . . . . . . . . . . . . . . . . . . 358
Line Mass Source . . . . . . . . . . . . . . . . . . . . . . 360
Point Mass Source . . . . . . . . . . . . . . . . . . . . . 360
Open Boundary . . . . . . . . . . . . . . . . . . . . . . 361
Thin Diffusion Barrier . . . . . . . . . . . . . . . . . . . . 361
Thin Impermeable Barrier . . . . . . . . . . . . . . . . . . 362
Equilibrium Reaction . . . . . . . . . . . . . . . . . . . . 362
Surface Reactions . . . . . . . . . . . . . . . . . . . . . 363
Surface Equilibrium Reaction . . . . . . . . . . . . . . . . . 364
Fast Irreversible Surface Reaction . . . . . . . . . . . . . . . 364
Porous Electrode Coupling . . . . . . . . . . . . . . . . . . 364
Reaction Coefficients . . . . . . . . . . . . . . . . . . . . 365
Electrode Surface Coupling . . . . . . . . . . . . . . . . . . 366
Porous Medium . . . . . . . . . . . . . . . . . . . . . . 366
Fluid . . . . . . . . . . . . . . . . . . . . . . . . . . 367
Porous Matrix . . . . . . . . . . . . . . . . . . . . . . . 368
Dispersion . . . . . . . . . . . . . . . . . . . . . . . . 369
Unsaturated Porous Medium . . . . . . . . . . . . . . . . . 370
Liquid . . . . . . . . . . . . . . . . . . . . . . . . . . 370
Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . 372
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . 373
Volatilization . . . . . . . . . . . . . . . . . . . . . . . 375
Species Source. . . . . . . . . . . . . . . . . . . . . . . 376
Hygroscopic Swelling . . . . . . . . . . . . . . . . . . . . 376
Out-of-Plane Flux . . . . . . . . . . . . . . . . . . . . . 377
Fracture . . . . . . . . . . . . . . . . . . . . . . . . . 379
Fluid (Fracture) . . . . . . . . . . . . . . . . . . . . . . 379
Fracture Material . . . . . . . . . . . . . . . . . . . . . . 380

The Transport of Diluted Species in Fractures Interface 381

Boundary, Edge, Point, and Pair Nodes for the Transport of Diluted
Species in Fractures Interface . . . . . . . . . . . . . . . . 383
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . 384
Concentration . . . . . . . . . . . . . . . . . . . . . . . 386
Dispersion . . . . . . . . . . . . . . . . . . . . . . . . 386
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 387
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 387
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 388

CONTENTS | 13
 Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 388
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 388
Species Source. . . . . . . . . . . . . . . . . . . . . . . 389

The Transport of Concentrated Species Interface 391

The Transport of Concentrated Species in Porous Media Interface . . . 397
Domain, Boundary, and Pair Nodes for the Transport of
Concentrated Species Interface . . . . . . . . . . . . . . . 398
Prescribing Conditions on Fluid-Solid Interfaces . . . . . . . . . . 399
Species Properties . . . . . . . . . . . . . . . . . . . . . 400
Transport Properties . . . . . . . . . . . . . . . . . . . . 400
Porous Medium . . . . . . . . . . . . . . . . . . . . . . 404
Fluid . . . . . . . . . . . . . . . . . . . . . . . . . . 404
Porous Matrix . . . . . . . . . . . . . . . . . . . . . . . 406
Electrode Surface Coupling . . . . . . . . . . . . . . . . . . 407
Reaction . . . . . . . . . . . . . . . . . . . . . . . . . 407
Reaction Sources . . . . . . . . . . . . . . . . . . . . . . 409
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 410
Mass Fraction . . . . . . . . . . . . . . . . . . . . . . . 411
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 411
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 413
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 414
Out-of-Plane Flux . . . . . . . . . . . . . . . . . . . . . 414
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 416
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 416
Flux Discontinuity . . . . . . . . . . . . . . . . . . . . . 417
Open Boundary . . . . . . . . . . . . . . . . . . . . . . 417
Equilibrium Reaction . . . . . . . . . . . . . . . . . . . . 418
Surface Equilibrium Reaction . . . . . . . . . . . . . . . . . 419

The Chemistry Interface 420

Feature Nodes Available for the Chemistry Interface . . . . . . . . 425
Reaction . . . . . . . . . . . . . . . . . . . . . . . . . 425
Species . . . . . . . . . . . . . . . . . . . . . . . . . 431
Electrode Reaction . . . . . . . . . . . . . . . . . . . . . 434
Electrode Reaction Group . . . . . . . . . . . . . . . . . . 436
Reversible Reaction Group . . . . . . . . . . . . . . . . . . 436
Equilibrium Reaction Group. . . . . . . . . . . . . . . . . . 438

14 | C O N T E N T S
Species Group . . . . . . . . . . . . . . . . . . . . . . . 439
Reaction Thermodynamics . . . . . . . . . . . . . . . . . . 439
Species Activity . . . . . . . . . . . . . . . . . . . . . . 439
Species Thermodynamics. . . . . . . . . . . . . . . . . . . 440

The Nernst–Planck–Poisson Equations Interface 441

The Electrophoretic Transport Interface 443

Common Settings for the Species Nodes in the Electrophoretic
Transport Interface . . . . . . . . . . . . . . . . . . . 446
Diffusion and Migration Settings . . . . . . . . . . . . . . . . 448
Domain, Boundary, and Pair Nodes for the Electrophoretic Transport
Interface. . . . . . . . . . . . . . . . . . . . . . . . 449
Solvent . . . . . . . . . . . . . . . . . . . . . . . . . 450
Porous Matrix Properties . . . . . . . . . . . . . . . . . . 450
Fully Dissociated Species . . . . . . . . . . . . . . . . . . . 450
Uncharged Species . . . . . . . . . . . . . . . . . . . . . 450
Weak Acid . . . . . . . . . . . . . . . . . . . . . . . . 451
Weak Base . . . . . . . . . . . . . . . . . . . . . . . . 451
Ampholyte . . . . . . . . . . . . . . . . . . . . . . . . 451
Protein . . . . . . . . . . . . . . . . . . . . . . . . . 452
Current Source . . . . . . . . . . . . . . . . . . . . . . 452
Initial Potential. . . . . . . . . . . . . . . . . . . . . . . 452
Current . . . . . . . . . . . . . . . . . . . . . . . . . 452
Current Density . . . . . . . . . . . . . . . . . . . . . . 452
Insulation . . . . . . . . . . . . . . . . . . . . . . . . . 453
Potential . . . . . . . . . . . . . . . . . . . . . . . . . 453
Species Source. . . . . . . . . . . . . . . . . . . . . . . 453
Initial Concentration . . . . . . . . . . . . . . . . . . . . 454
Concentration . . . . . . . . . . . . . . . . . . . . . . . 454
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 454
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 454
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 455
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 455

The Surface Reactions Interface 456

Boundary, Edge, Point, and Pair Nodes for the Surface Reactions
Interface. . . . . . . . . . . . . . . . . . . . . . . . 457

CONTENTS | 15
 Surface Properties . . . . . . . . . . . . . . . . . . . . . 458
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 459
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 459
Surface Concentration . . . . . . . . . . . . . . . . . . . . 460

The Reacting Flow Interfaces 461

The Reacting Laminar Flow Interface . . . . . . . . . . . . . . 461
The Reacting Flow Coupling Feature . . . . . . . . . . . . . . 462
Physics Interface Features . . . . . . . . . . . . . . . . . . 466

The Reacting Flow in Porous Media Interfaces 468

The Reacting Flow in Porous Media, Transport of Diluted Species
Interface. . . . . . . . . . . . . . . . . . . . . . . . 468
The Reacting Flow in Porous Media, Transport of Concentrated
Species Interface. . . . . . . . . . . . . . . . . . . . . 469
The Reacting Flow, Diluted Species Coupling Feature . . . . . . . . 469
The Reacting Flow Coupling Feature . . . . . . . . . . . . . . 470
Physics Interface Features . . . . . . . . . . . . . . . . . . 470

The Nonisothermal Reacting Flow Multiphysics Interfaces 471

The Nonisothermal Reacting Laminar Flow Interface . . . . . . . . . 471
The Nonisothermal Reacting Turbulent Flow, k-ε Interface. . . . . . 472
The Nonisothermal Reacting Turbulent Flow, k-ω Interface . . . . . 473
The Nonisothermal Reacting Turbulent Flow, SST Interface . . . . . 474
The Nonisothermal Reacting Turbulent Flow, Low Re k-ε Interface . . 475
The Reacting Flow Coupling Feature . . . . . . . . . . . . . . 476
Physics Interface Features . . . . . . . . . . . . . . . . . . 477

Theory for the Transport of Diluted Species Interface 478

Mass Balance Equation . . . . . . . . . . . . . . . . . . . . 479
Equilibrium Reaction Theory . . . . . . . . . . . . . . . . . 480
Convective Term Formulation. . . . . . . . . . . . . . . . . 482
Solving a Diffusion Equation Only . . . . . . . . . . . . . . . 483
Mass Sources for Species Transport . . . . . . . . . . . . . . 483
Adding Transport Through Migration . . . . . . . . . . . . . . 485
Supporting Electrolytes . . . . . . . . . . . . . . . . . . . 486
Crosswind Diffusion . . . . . . . . . . . . . . . . . . . . 487
Danckwerts Inflow Boundary Condition . . . . . . . . . . . . . 488

16 | C O N T E N T S
Mass Balance Equation for Transport of Diluted Species in Porous
Media . . . . . . . . . . . . . . . . . . . . . . . . . 489
Convection in Porous Media . . . . . . . . . . . . . . . . . 490
Diffusion in Porous Media . . . . . . . . . . . . . . . . . . 492
Dispersion . . . . . . . . . . . . . . . . . . . . . . . . 493
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . 495
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 497
Mass Transport in Fractures . . . . . . . . . . . . . . . . . 498
References . . . . . . . . . . . . . . . . . . . . . . . . 499

Theory for the Transport of Concentrated Species Interface 501

Multicomponent Mass Transport . . . . . . . . . . . . . . . . 501
Multicomponent Gas Diffusion: Maxwell–Stefan Description . . . . . 502
Multicomponent Diffusivities . . . . . . . . . . . . . . . . . 504
Multicomponent Diffusion: Mixture-Averaged Approximation . . . . . 506
Multispecies Diffusion: Fick’s Law Approximation . . . . . . . . . 508
Multicomponent Thermal Diffusion . . . . . . . . . . . . . . . 509
Regularization of Reaction Rate Expression . . . . . . . . . . . . 509
References for the Transport of Concentrated Species Interface . . . . 510

Theory for the Electrophoretic Transport Interface 511

Theory for the Surface Reactions Interface 517

Governing Equations for the Surface Concentrations . . . . . . . . 517
Governing Equations for the Bulk Concentrations . . . . . . . . . 518
ODE Formulations for Surface Concentrations . . . . . . . . . . 520
Surface Reaction Equations on Deforming Geometries . . . . . . . 521
Reference for the Surface Reactions Interface . . . . . . . . . . . 522

Theory for the Coupling of Mass Transport to

Electrochemical Reactions 523
Molar Sources and Sinks . . . . . . . . . . . . . . . . . . . 523
Mass Sources and Sinks . . . . . . . . . . . . . . . . . . . 524

Theory for the Reacting Flow Interface 525

Pseudo Time Stepping for Mass Transport . . . . . . . . . . . . 525
The Stefan Velocity . . . . . . . . . . . . . . . . . . . . . 525
The Chemical Reaction Rate . . . . . . . . . . . . . . . . . 527

CONTENTS | 17
 Chapter 7: Fluid Flow Interfaces

The Laminar Flow and Creeping Flow Interfaces 530

The Creeping Flow Interface . . . . . . . . . . . . . . . . . 530
The Laminar Flow Interface . . . . . . . . . . . . . . . . . . 531
Domain, Boundary, Pair, and Point Nodes for Single-Phase Flow . . . . . 537
Fluid Properties . . . . . . . . . . . . . . . . . . . . . . 537
Volume Force . . . . . . . . . . . . . . . . . . . . . . . 539
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 539
Wall . . . . . . . . . . . . . . . . . . . . . . . . . . 540
Inlet . . . . . . . . . . . . . . . . . . . . . . . . . . . 543
Outlet . . . . . . . . . . . . . . . . . . . . . . . . . . 547
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 550
Open Boundary . . . . . . . . . . . . . . . . . . . . . . 550
Boundary Stress . . . . . . . . . . . . . . . . . . . . . . 551
Periodic Flow Condition . . . . . . . . . . . . . . . . . . . 553
Flow Continuity . . . . . . . . . . . . . . . . . . . . . . 555
Pressure Point Constraint . . . . . . . . . . . . . . . . . . 555
Point Mass Source . . . . . . . . . . . . . . . . . . . . . 556
Line Mass Source . . . . . . . . . . . . . . . . . . . . . . 556
Gravity . . . . . . . . . . . . . . . . . . . . . . . . . 557

The Darcy’s Law Interface 558

Domain, Boundary, Edge, Point, and Pair Nodes for the Darcy’s
Law Interface . . . . . . . . . . . . . . . . . . . . . . 560
Porous Medium . . . . . . . . . . . . . . . . . . . . . . 562
Fluid . . . . . . . . . . . . . . . . . . . . . . . . . . 564
Porous Matrix . . . . . . . . . . . . . . . . . . . . . . . 565
Mass Source . . . . . . . . . . . . . . . . . . . . . . . 567
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 568
Unsaturated Porous Medium . . . . . . . . . . . . . . . . . 568
Gravity . . . . . . . . . . . . . . . . . . . . . . . . . 570
Cross Section . . . . . . . . . . . . . . . . . . . . . . . 570
Thickness. . . . . . . . . . . . . . . . . . . . . . . . . 571
Porous Electrode Coupling . . . . . . . . . . . . . . . . . . 571
Electrode Surface Coupling . . . . . . . . . . . . . . . . . . 571
Pressure . . . . . . . . . . . . . . . . . . . . . . . . . 572

18 | C O N T E N T S
Mass Flux. . . . . . . . . . . . . . . . . . . . . . . . . 572
Line Mass Source . . . . . . . . . . . . . . . . . . . . . . 573
Point Mass Source . . . . . . . . . . . . . . . . . . . . . 574
Inlet . . . . . . . . . . . . . . . . . . . . . . . . . . . 574
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 575
No Flow . . . . . . . . . . . . . . . . . . . . . . . . . 576
Flux Discontinuity . . . . . . . . . . . . . . . . . . . . . 576
Outlet . . . . . . . . . . . . . . . . . . . . . . . . . . 577
Precipitation . . . . . . . . . . . . . . . . . . . . . . . 577
Interior Wall . . . . . . . . . . . . . . . . . . . . . . . 577
Thin Barrier. . . . . . . . . . . . . . . . . . . . . . . . 578
Pressure Head . . . . . . . . . . . . . . . . . . . . . . . 578
Hydraulic Head . . . . . . . . . . . . . . . . . . . . . . 578
Atmosphere/Gauge . . . . . . . . . . . . . . . . . . . . . 579
Pervious Layer . . . . . . . . . . . . . . . . . . . . . . . 579
Well . . . . . . . . . . . . . . . . . . . . . . . . . . 581
Fracture . . . . . . . . . . . . . . . . . . . . . . . . . 581
Fluid (Fracture) . . . . . . . . . . . . . . . . . . . . . . 584
Fracture Material . . . . . . . . . . . . . . . . . . . . . . 584

The Free and Porous Media Flow Interface 587

Domain, Boundary, Point, and Pair Nodes for the Free and Porous
Media Flow Interface . . . . . . . . . . . . . . . . . . . 589
Fluid Properties . . . . . . . . . . . . . . . . . . . . . . 590
Porous Medium . . . . . . . . . . . . . . . . . . . . . . 591
Fluid . . . . . . . . . . . . . . . . . . . . . . . . . . 591
Porous Matrix . . . . . . . . . . . . . . . . . . . . . . . 592
Mass Source . . . . . . . . . . . . . . . . . . . . . . . 593
Volume Force . . . . . . . . . . . . . . . . . . . . . . . 593
Porous Electrode Coupling . . . . . . . . . . . . . . . . . . 594
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 594
Gravity . . . . . . . . . . . . . . . . . . . . . . . . . 594
Electrode-Electrolyte Interface Coupling . . . . . . . . . . . . . 595
Wall . . . . . . . . . . . . . . . . . . . . . . . . . . 595

The Brinkman Equations Interface 597

Domain, Boundary, Point, and Pair Nodes for the Brinkman
Equations Interface . . . . . . . . . . . . . . . . . . . . 600

CONTENTS | 19
 Porous Medium . . . . . . . . . . . . . . . . . . . . . . 601
Fluid . . . . . . . . . . . . . . . . . . . . . . . . . . 602
Porous Matrix . . . . . . . . . . . . . . . . . . . . . . . 603
Mass Source . . . . . . . . . . . . . . . . . . . . . . . 604
Volume Force . . . . . . . . . . . . . . . . . . . . . . . 605
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 605
Fluid Properties . . . . . . . . . . . . . . . . . . . . . . 605
Gravity . . . . . . . . . . . . . . . . . . . . . . . . . 606

Theory for the Laminar Flow and Creeping Flow Interfaces 608
General Single-Phase Flow Theory . . . . . . . . . . . . . . . 609
Compressible Flow . . . . . . . . . . . . . . . . . . . . . 611
Weakly Compressible Flow . . . . . . . . . . . . . . . . . . 611
The Mach Number Limit . . . . . . . . . . . . . . . . . . . 611
Incompressible Flow . . . . . . . . . . . . . . . . . . . . 612
The Reynolds Number. . . . . . . . . . . . . . . . . . . . 613
Gravity . . . . . . . . . . . . . . . . . . . . . . . . . 614
Theory for the Wall Boundary Condition . . . . . . . . . . . . 615
Prescribing Inlet and Outlet Conditions . . . . . . . . . . . . . 619
Mass Flow . . . . . . . . . . . . . . . . . . . . . . . . 621
Fully Developed Flow (Inlet) . . . . . . . . . . . . . . . . . 623
Fully Developed Flow (Outlet). . . . . . . . . . . . . . . . . 624
No Viscous Stress . . . . . . . . . . . . . . . . . . . . . 625
Normal Stress Boundary Condition . . . . . . . . . . . . . . . 626
Pressure Boundary Condition . . . . . . . . . . . . . . . . . 626
Mass Sources for Fluid Flow . . . . . . . . . . . . . . . . . 629
Numerical Stability — Stabilization Techniques for Fluid Flow . . . . . 631
Solvers for Laminar Flow . . . . . . . . . . . . . . . . . . . 633
Pseudo Time Stepping for Laminar Flow Models . . . . . . . . . . 635
Discontinuous Galerkin Formulation . . . . . . . . . . . . . . 637
Particle Tracing in Fluid Flow . . . . . . . . . . . . . . . . . 637
References for the Single-Phase Flow, Laminar Flow Interfaces . . . . 638

Theory for the Darcy’s Law Interface 641

About Darcy’s Law . . . . . . . . . . . . . . . . . . . . . 641
Darcy’s Law — Equation Formulation . . . . . . . . . . . . . . 642
Storage Model . . . . . . . . . . . . . . . . . . . . . . . 643
Average Linear Velocity . . . . . . . . . . . . . . . . . . . 644

20 | C O N T E N T S
 References for the Darcy’s Law Interface. . . . . . . . . . . . . 644

Theory for the Free and Porous Media Flow Interface 646
Reference for the Free and Porous Media Flow Interface. . . . . . . 646

Theory for the Brinkman Equations Interface 647

About the Brinkman Equations . . . . . . . . . . . . . . . . 647
Brinkman Equations Theory. . . . . . . . . . . . . . . . . . 647
References for the Brinkman Equations Interface. . . . . . . . . . 649

Theory for the Coupling of Fluid Flow to Electrochemical

Reactions 650
Momentum Sources and Sinks . . . . . . . . . . . . . . . . . . 650

Chapter 8: Heat Transfer

Coupling of Heat Transfer to Electrochemical Reactions 652

Joule Heating Due to Charge Transport . . . . . . . . . . . . . 653
Heating Due to Electrochemical Reactions . . . . . . . . . . . . 653
Heating Due to Heat of Mixing . . . . . . . . . . . . . . . . 654
Heat of Mixing in Intercalating Electrodes . . . . . . . . . . . . 655
Total Overpotential Calculation for Concentration Dependent Kinetics . 656
References . . . . . . . . . . . . . . . . . . . . . . . . 657

Chapter 9: Solid Mechanics

Chapter 10: Thermodynamics

Using Thermodynamic Properties 664

Workflow for Thermodynamics Property Calculations . . . . . . . 664
Thermodynamics . . . . . . . . . . . . . . . . . . . . . . 666
Thermodynamic System . . . . . . . . . . . . . . . . . . . 667
External Thermodynamic Packages . . . . . . . . . . . . . . . 675

CONTENTS | 21
 External Thermodynamic System . . . . . . . . . . . . . . . . 676
Predefined System . . . . . . . . . . . . . . . . . . . . . 679
Exporting and Importing Thermodynamic Systems . . . . . . . . . 682
Species Property . . . . . . . . . . . . . . . . . . . . . . 683
Mixture Property. . . . . . . . . . . . . . . . . . . . . . 689
Equilibrium Calculation . . . . . . . . . . . . . . . . . . . 690
Generate Chemistry . . . . . . . . . . . . . . . . . . . . 694
Generate Material . . . . . . . . . . . . . . . . . . . . . 696
Coupling with the Reaction Engineering and the Chemistry Interfaces . . 700
Evaluating a Property Function in a Physics Interface . . . . . . . . 705
User-Defined Species . . . . . . . . . . . . . . . . . . . . 705
References . . . . . . . . . . . . . . . . . . . . . . . . 711

Thermodynamic Models and Theory 712

Introduction . . . . . . . . . . . . . . . . . . . . . . . 712
Thermodynamic Models . . . . . . . . . . . . . . . . . . . 712
Selecting the Right Thermodynamic Model . . . . . . . . . . . . 727
Species Property References . . . . . . . . . . . . . . . . . 728
Thermodynamic Properties Definitions . . . . . . . . . . . . . 728
Standard Enthalpy of Formation and Absolute Entropy Terms . . . . . 732
Reference State . . . . . . . . . . . . . . . . . . . . . . 734
Transport Properties . . . . . . . . . . . . . . . . . . . . 734
Surface Tension . . . . . . . . . . . . . . . . . . . . . . 760
References . . . . . . . . . . . . . . . . . . . . . . . . 760

Chapter 11: Multiphysics Coupling Nodes

Deforming Electrode Surface . . . . . . . . . . . . . . . . . 770
Nondeforming Boundary . . . . . . . . . . . . . . . . . . . 771
Electrochemical Heating . . . . . . . . . . . . . . . . . . . 772
Potential Coupling . . . . . . . . . . . . . . . . . . . . . 772
Space Charge Density Coupling . . . . . . . . . . . . . . . . 772

22 | C O N T E N T S
Chapter 12: Parameter Estimation

Chapter 13: Glossary

Glossary of Terms 776

CONTENTS | 23
24 | C O N T E N T S
 1

Introduction

This guide describes the Battery Design Module, an optional add-on package for
COMSOL Multiphysics® designed to assist you in building detailed models of the
configuration of the electrodes, separators, current collectors and other
components of battery 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 Battery Design Module

• Overview of the User’s Guide

25
 About the Battery Design Module
In this section:

• What Can the Battery Design Module Do?

• Battery Design Module Physics Interface Guide
• Common Physics Interface and Feature Settings and Nodes
• Where Do I Access the Documentation and Application Libraries?

What Can the Battery Design Module Do?

The Battery Design Module extends the COMSOL Multiphysics environment with
customized physics interfaces for modeling of batteries. These physics interfaces
provide tools for building detailed models of the configuration of the various
components of a battery. The physics interfaces include descriptions of the
electrochemical reactions and the transport properties that influence the performance
in terms of charge-discharge characteristics, capacity, heat production and capacity
fade. With this module, you have the perfect tools to investigate the influence of using
different materials, geometric configurations, and operating conditions.

The core functionality of the module are the electrochemistry interfaces. Generic
electrochemistry interfaces for various types (primary, secondary and tertiary) current
distributions are available, which may be used for modeling both solid nonporous as
well as for porous electrodes. In addition to these generic electrochemistry interfaces,
the module also contains dedicated battery interfaces.

The tailored physics interfaces mentioned above are also complemented with extended
functionality in other physics interfaces for chemical species transport, heat transfer,
and fluid flow. The extended functionality for heat transfer and fluid flow may be used,
for instance, in battery thermal management models.

A selection of suitable materials are also available in the Battery Material

Library. For more detailed information about materials, see Materials in
the COMSOL Multiphysics Reference Manual.

26 | CHAPTER 1: INTRODUCTION
 Finally, the Application Library available with Battery Design Module includes various
tutorials (model examples), for a multitude of different battery chemistries such as:

• Lithium-ion (Li-ion) batteries

• Lead–Acid batteries
• Nickel–metal hydride (NiMH) batteries
• Vanadium redox flow batteries
• Soluble lead–acid flow batteries

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.

Battery Design 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.

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

ABOUT THE BATTERY DESIGN MODULE | 27

 PHYSICS INTERFACE ICON TAG SPACE AVAILABLE STUDY TYPE
DIMENSION

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
Transport of tcs all dimensions stationary; time dependent
Concentrated Species in
Porous Media
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

Nonisothermal Reacting Flow

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

axisymmetric
Reacting Flow in Porous Media

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

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

28 | 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
Battery Interfaces

Lithium-Ion Battery liion all dimensions stationary; time dependent;

(Binary 1:1 Liquid AC impedance, initial
Electrolyte, values; AC impedance,
stationary; AC impedance,
Single-Ion Conductor)
time dependent
Battery with Binary batbe all dimensions stationary; time dependent;
Electrolyte AC impedance, initial
values; AC impedance,
stationary; AC impedance,
time dependent

ABOUT THE BATTERY DESIGN MODULE | 29

 PHYSICS INTERFACE ICON TAG SPACE AVAILABLE STUDY TYPE
DIMENSION

Lead–Acid Battery leadbat all dimensions stationary; time dependent;

AC impedance, initial
values; AC impedance,
stationary; AC impedance,
time dependent
Single Particle Battery spb all dimensions time dependent; time
dependent with
initialization
Lumped Battery lb all dimensions time dependent; AC
impedance, initial values;
Battery Equivalent ec Not space stationary; time dependent;
Circuit dependent frequency domain
Battery Pack bp 3D time dependent

Fluid Flow

Porous Media and Subsurface Flow

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

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

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

Flow axisymmetric
Nonisothermal Flow

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

axisymmetric stationary, one-way NITF;
time dependent, one-way
NITF
Heat Transfer

Heat Transfer in ht all dimensions stationary; time dependent

Porous Media

30 | 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 online 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 on how to use COMSOL Multiphysics and how to access the electronic
Documentation and Help content.

ABOUT THE BATTERY DESIGN MODULE | 31

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

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 will be sent to you
by email. You can also access technical support, software updates, license information,
and other resources by registering for a COMSOL Access account.

COMSOL ONLINE RESOURCES

COMSOL website www.comsol.com

Contact COMSOL www.comsol.com/contact
COMSOL Access www.comsol.com/access

32 | CHAPTER 1: INTRODUCTION
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/forum
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 BATTERY DESIGN MODULE | 33

 Overview of the User’s Guide
The Battery Design 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 BATTERY INTERFACES

The Battery Interfaces chapter describes the Battery with Binary Electrolyte, Lead–
Acid Battery, and Lumped Battery, the Single-Particle Battery and the Lithium-Ion
Battery interfaces. Also the Battery Equivalent Circuit model wizard entry is described
in this chapter.

THE ELECTROCHEMISTRY INTERFACES

The Electrochemistry Interfaces chapter describes the Primary Current Distribution,
Secondary Current Distribution, Tertiary Current Distribution, Nernst-Planck,
Electrode, Shell, and Electroanalysis interfaces.

THE AC/DC INTERFACES

The AC/DC Interfaces chapter describes the Electrostatics, the Electrical Currents
and the Electrical Circuit interfaces.

34 | CHAPTER 1: INTRODUCTION
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, the Surface Reaction and the Reacting Flow interfaces.

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.

HEAT TRANSFER
The Heat Transfer chapter describes how electrochemical heat sources can be coupled
to heat transfer, and the theory for how these are calculated.

SOLID MECHANICS
The Solid Mechanics chapter describes functionality added by the Battery Design
Module to the Solid Mechanics interface.

THERMODYNAMICS
This chapter describes the functionality of the Thermodynamics node to define
thermo-physical and transport properties.

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 | 35

36 | CHAPTER 1: INTRODUCTION
 2

Modeling with Electrochemistry

In this chapter:
• Introduction to Electrochemistry Modeling
• Connecting to Electrical Circuits
• SPICE Import and Export

37
 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
• Battery Modeling
• Modeling Cyclic Voltammetry
• Common Simplifications When Modeling Electrochemical Cells
• Before You Start Building Your Model
• Meshing Advice
• Solving Electrochemical Models
• Postprocessing Your Solution

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

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

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

38 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

Electrochemical Applications
Electrochemical systems may be classified in different ways.

One approach is to contrast those electrochemical systems involving desirable reactions

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

Corrosion is an example of undesirable electrochemistry because in this case

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

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

The different electrochemical modules in COMSOL Multiphysics are designed to

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

Fundamentals of Electrochemistry Modeling

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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 39

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

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

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

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

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

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

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

OUTPUTS OF INTEREST FROM A MODEL

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

40 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

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

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

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

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

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

Polarization curves are frequently nonlinear. The combination of nonlinearity and

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

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

Current Distribution Cases and Choosing the Right Interface to

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

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

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

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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 41

 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

42 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

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

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

∇ ⋅ D = ρv

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

D = ε 0 ε s E = – ε 0 ε s ∇V

Hence

2 ρv
∇ V + ---------- = 0
ε0 εs

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

ρv = F  zi ci
i

Hence

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

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

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

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

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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 43

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

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

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

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

• Theory for the Transport of Diluted Species Interface

• Theory of Electrostatics in the COMSOL Multiphysics Reference
Manual

An important dimensional quantity occurring in the Poisson equation is:

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

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

 zi ci = 0

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

potential in the Nernst–Planck equations, in place of the full Poisson equation. The

44 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

Nernst–Planck equations with electroneutrality are used to describe current flow in the
Tertiary Current Distribution, Nernst-Planck interface.

The Tertiary Current Distribution, Nernst-Planck Interface

The current flow itself is given by:

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

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

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

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

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

Hence, it follows that:

i l = – σ l ∇φ l

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

2
F
 zi
2
σ l = -------- Di ci
RT

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 45

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

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

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

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

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

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

Theory for the Current Distribution Interfaces

Modeling Electrochemical Reactions

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

46 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

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

+ -
Ag (aq)+e ↔ Ag(s)

This reaction is called a “half-cell” reaction, since it will occur at a specific

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

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

ΔG m
E eq, m = – -------------
nm F

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

Equilibrium potentials should always be quoted versus a specific

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

From the standard thermodynamic relation

ΔG = – RT ln K

it follows

RT
E – E eq = -------- ln K
nF

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

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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 47

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

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

nF
RT

Hence at equilibrium, the concentrations of reactants and products at the

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

The quantity

η m = φ s – φ l – E eq, m

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

interface.

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

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

KINETICS OF ELECTROCHEMICAL REACTIONS

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

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

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

48 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

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

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

log  ---- = Aη
i
i0

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

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

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

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

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

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

highly adaptable because:

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

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

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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 49

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

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

Using a linearized Butler-Volmer reaction can be advantageous when

investigating convergence issues of a model.

The linearized Butler-Volmer equation is not correct for applied

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

Electrode Kinetics Expressions

FLUXES AND SOURCES/SINKS DUE TO ELECTRODE REACTIONS

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

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

The mathematical treatment can be summed up by the expression:

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

50 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

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

As such, knowledge of the stoichiometry of an electrochemical reaction allows the local

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

The stoichiometric coefficients of the chemical species in an

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

COMSOL Multiphysics uses the standard convention that anodic

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

DEFINING CONCENTRATION DEPENDENT BUTLER-VOLMER KINETICS

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

-
Ox + ne ↔ Red (2-1)

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

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

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

E = φs – φl (2-3)

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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 51

 αa + αc = n (2-4)

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

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

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

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

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

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

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

η = E – E eq (2-7)

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

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

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

Typically standard conditions are used as reference concentrations, for instance

concentrations of 1 M for ions in aqueous solutions.

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

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

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

52 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

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

where

η ref = E – E eq,ref (2-10)

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

Double Layer Capacitance

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

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

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

i tot = i Far + i NF

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

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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 53

 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

54 | 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 | 55

 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

Battery Modeling
Batteries are electrochemical energy extraction/storage 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. 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.

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 ΔG).

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.

56 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

Generic battery models can be set up using the Tertiary Current Distribution interface
to describe charge transport coupled to species transport is required.

The Lumped Battery interface and Battery Equivalent Circuit interfaces are general
“black box”-approach interfaces, which make use of global equations and parameters,
typically fitted to experimental data, for capturing the battery cell dynamic
charge-discharge behavior.

The Single Particle Battery interface is a generic interface for modeling intercalation
electrode-based batteries. It may be viewed as a semi-lumped version of the
Lithium--on and Battery with Binary Electrolyte interfaces described below.

TAILOR MADE 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 comproportionation of Pb(0) and Pb(IV) through a sulfuric acid medium.

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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 57

 of interest, allowing both the kinetics and transport properties of the chemical species
to be investigated. The target species reacts under kinetic control to the point of
depletion where the current becomes transport-controlled.

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

Common Simplifications When Modeling Electrochemical Cells

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

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

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

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

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

58 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

potential can be much lower in this type of electrodes. This is done in the Porous
Electrode nodes.

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

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

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

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

REPLACING THIN LAYERS WITH BOUNDARY CONDITIONS

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

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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 59

 twenty-five times the electrode size - assuming that the surrounding electrolyte is
uniform. Applying a bulk boundary condition such as a fixed concentration at this
finite distance causes inaccuracy in the solution, however.

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

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

COMSOL Multiphysics Reference Manual

Before You Start Building Your Model

INTRODUCING COMPLEXITY ONE STEP AT A TIME

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

60 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

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

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.

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 61

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

Meshing in the COMSOL Multiphysics Reference Manual

Solving Electrochemical Models

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

GENERAL CURRENT DISTRIBUTION PROBLEMS

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

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

62 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

 not solve with nonlinear kinetics, thereby indicating suitable initial values for the
nonlinear problem.
• If your model contains porous electrodes, try refining the mesh resolution in these
domains, especially toward the electrolyte boundaries.

• Electrochemistry Interfaces
• Specifying Initial Values and Inspecting and Troubleshooting Meshes
in the COMSOL Multiphysics Reference Manual

ELECTROCHEMISTRY COUPLED TO MASS TRANSPORT

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

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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 63

 convergence issues occur, the current load of the model is too high in relation to
your initial concentrations or mass transport properties.

• Electrochemistry Interfaces
In the COMSOL Multiphysics Reference Manual:

• 2D and 3D Boundary Layer Meshes

• Stationary and Parametric Sweep

SETTING UP A STUDY SEQUENCE FOR MULTIPHYSICS PROBLEMS

For multiphysics problems, try to adjust the study sequence.

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

64 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

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

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

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

• Double Layer Capacitance

In the COMSOL Multiphysics Reference Manual:

• Step and Time Dependent

• Building a COMSOL Multiphysics Model and The Events Interface

SOLVER SETTINGS
Try adjusting the solver settings.

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

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

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 65

 Electrochemistry Studies and Study Steps and Cyclic Voltammetry in the
COMSOL Multiphysics Reference Manual

In multicomponent systems it is rarely straightforward to predict the rest

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

Electrochemistry Studies and Study Steps in the COMSOL Multiphysics

Reference Manual

Studies and Solvers and Building a COMSOL Multiphysics Model in the

COMSOL Multiphysics Reference Manual

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

66 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

TABLE 2-1: COMMON POTENTIAL VARIABLES

VARIABLE DESCRIPTION DEFINED AT

xxx.Eeq_yy Equilibrium potential Electrode Reaction boundaries

and Porous Electrode Reaction
domains
xxx.eta_yy Overpotential Electrode Reaction boundaries
The unit is V for all the above variables.
xxx denotes the tag of the physics interface. For instance, cd for the Secondary Current Distribution inter-
face.
yy denotes the tag of the (Porous) Electrode Reaction node, for instance, er1 for an Electrode Reaction
node.

CURRENT VARIABLES AND CALCULATING THE TOTAL CELL CURRENT

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

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

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

VARIABLE UNIT DESCRIPTION DEFINED AT

xxx.nIl A/m2 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)

INTRODUCTION TO ELECTROCHEMISTRY MODELING | 67

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

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

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

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

In the COMSOL Multiphysics Reference Manual:

• Nonlocal Couplings and Coupling Operators and Integration

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

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

68 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

Connecting to Electrical Circuits
In this section:

• About Connecting Electrical Circuits to Physics Interfaces

• Connecting Electrical Circuits Using Predefined Couplings
• Connecting Electrical Circuits by User-Defined Couplings
• Solving
• Postprocessing

About Connecting Electrical Circuits to Physics Interfaces

This section describes the various ways electrical circuits can be connected to other
physics interfaces in COMSOL Multiphysics. If you are not familiar with circuit
modeling, it is recommended that you review the Theory for the Electrical Circuit
Interface.

In general electrical circuits connect to other physics interfaces via one or more of three
special circuit features:

• External I vs. U
• External U vs. I
• External I-Terminal

These features either accept a voltage measurement from the connecting noncircuit
physics interface and return a current from an Battery or Current Distribution
Interface (or an Electrical Circuit interface), or the other way around.

The “External” features are considered “ideal” current or voltage sources

by the Electrical Circuit interface. Hence, you cannot connect them
directly in parallel (voltage sources) or in series (current sources) with
other ideal sources. This results in the error message The DAE is
structurally inconsistent. A workaround is to provide a suitable parallel
or series resistor, which can be tuned to minimize its influence on the
results.

CONNECTING TO ELECTRICAL CIRCUITS | 69

 Connecting Electrical Circuits Using Predefined Couplings
In addition to these circuit features, interfaces in the AC/DC Module, RF Module,
MEMS Module, Plasma Module, and Semiconductor Module (the modules that
include the Electrical Circuit interface) also contain features that provide couplings to
the Electrical Circuit interface by accepting a voltage or a current from one of the
specific circuit features (External I vs. U, External U vs. I, and External I-Terminal).

This coupling is typically activated when:

• A choice is made in the Settings window for the noncircuit physics interface feature,
which then announces (that is, includes) the coupling to the Battery or Current
Distribution (or Electrical Circuit) interface. Its voltage is then included to make it
visible to the connecting circuit feature.
• A voltage that has been announced (that is, included) is selected in a feature node’s
Settings window.

These circuit connections are supported in Circuit Terminals.

Connecting Electrical Circuits by User-Defined Couplings

A more general way to connect a physics interface to the Electrical Circuit interface is
to:

• Apply the voltage or current from the connecting “External” circuit feature as an
excitation in the noncircuit physics interface.
• Define your own voltage or current measurement in the noncircuit physics interface
using variables, coupling operators and so forth.
• In the Settings window for the Electrical Circuit interface feature, selecting the
User-defined option and entering the name of the variable or expression using
coupling operators defined in the previous step.

DETERMINING A CURRENT OR VOLTAGE VARIABLE NAME

To determine a current or voltage variable name, look at the Dependent Variables node
under the Study node. To do this:

1 In the Model Builder, right-click the Study node and select Show Default Solver.

70 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

2 Expand the Solver>Dependent Variables node and click the state node, in this
example, Current through device R1 (comp1.currents). The variable name is shown in
the Settings window for State.

Typically, voltage variables are named cir.Xn_v and current variables

cir.Xn_i, where n is the “External” device number — 1, 2, and so on.

Solving

Some modeling errors lead to the error message The DAE is structurally
inconsistent being displayed when solving. This error typically occurs
from having an open current loop, from connecting voltage sources in
parallel, or connecting current sources in series.

In this respect, the predefined coupling features are also treated as (ideal)
voltage or current sources. The remedy is to close current loops and to
connect resistors in series with voltage sources or in parallel with current
sources.

CONNECTING TO ELECTRICAL CIRCUITS | 71

 Postprocessing
The Electrical Circuits interface, unlike most of the other physics interfaces, solves for
a relatively large number of global dependent variables (such as voltages and currents),
instead of solving for a few space-varying fields (such as temperature or displacement).
For this reason, the Electrical Circuit interface does not provide default plots when
computing a study.

The physics interface defines a number of variables that can be used in postprocessing.
All variables defined by the Electrical Circuit interface are of a global scope, and can
be evaluated in a Global Evaluation node (under Derived Values). In addition, the time
evolution or dependency on a parameter can be plotted in a Global plot (under a 1D
Plot Group node).

The physics interface defines a Node voltage variable for each electrical node in the
circuit, with name cir.v_name, where cir is the physics interface Label and <name>
is the node Name. For each two-pin component, the physics interface also defines
variables containing the voltage across it and the current flowing through it.

In the COMSOL Multiphysics Reference Manual:

• Derived Values, Evaluation Groups, and Tables and Global Evaluation

• Plot Groups and Plots and Global

References
1. V. Kaajakari, Practical MEMS, Small Gear Publishing, Las Vegas, 2009.

2. S.D. Senturia, Microsystem Design, Springer Science and Business Media, New
York, 2001.

3. A.F. Bower, Applied Mechanics of Solids, CRC Press, Boca Raton, FL, 2010
(http://www.solidmechanics.org).

72 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

S P IC E I m po r t an d E xp ort
The following text is a generic description of the SPICE Import and Export
functionality available with various add-on products from COMSOL.

SPICE Import
The circuit definition in COMSOL Multiphysics adheres to the SPICE format
developed at the University of California, Berkeley (Ref. 1). SPICE netlists can be
imported and the corresponding circuit nodes are generated in the COMSOL
Multiphysics model. Most circuit simulators can export to this format or some version
of it.

The Electrical Circuit interface supports the following device models:

TABLE 2-3: SUPPORTED SPICE DEVICE MODELS

STATEMENT DEVICE MODEL

R Resistor
C Capacitor
L Inductor
V Voltage Source
I Current Source
E Voltage-Controlled Voltage Source
F Current-Controlled Voltage Source
G Voltage-Controlled Current Source
H Current-Controlled Voltage Source
D Diode
Q NPN BJT and PNP BJT
M n-Channel MOSFET and p-Channel MOSFET
X Subcircuit Instance

Statements corresponding to multiple devices are resolved by parsing the associated

.model statement. The physics interface also supports the .subckt statement, which
is represented in COMSOL by a Subcircuit Definition node, and the .include
statement. SPICE commands are interpreted case-insensitively. The statement defining
each device is also interpreted as the Device name.

SPICE IMPORT AND EXPORT | 73

 According to SPICE specification, the first line in the netlist file is assumed to be the
title of the netlist and it is ignored by the parser.

SPICE Export
The SPICE Export functionality creates a SPICE netlist file containing a description of
the circuit represented by the physics interface. This functionality can be accessed from
the physics interface context menu (right-click the physics interface node and select
Export SPICE Netlist). After specifying a filename, the circuit is exported and messages
from the export process display in the Messages window. During the export process, a
series of operations are performed:

• In order to avoid conflicts, each component must be identified by a unique Device

name. If one or more components have the same device name, the export operation
fails and an error message is displayed. All characters in a Device name that are not
letters, digits or underscores are replaced by underscores.
• According to the SPICE specification, each circuit must have a node with name 0,
which is assumed to be the only ground node. When exporting a circuit, any node
with name 0 that is not connected to a Ground component is exported with a
different node name. All nodes that are connected to a Ground components are
exported as a merged node with name 0. The Messages window shows a log message
if these operations are performed, showing the name of the renamed or merged
nodes.
• All characters in node names that are not letters, digits or underscores are replaced
by underscores.
• Some components (most notably, the External components used to couple to other
physics interfaces) cannot be exported to a SPICE netlist. These components are
ignored during the export process, and a message is shown in the Messages window.
Note that this can change the exported circuit, since some components are then
missing.
• Subcircuit definitions are added as .subckt statements in the netlist.
Semiconductor devices (such as MOSFETs, BJTs, and diodes) are exported as a
SPICE device with a corresponding .model statement.

The title of the exported netlist file is the model’s filename, and the time, date, and
version of COMSOL Multiphysics is added as a comment in the netlist file.

74 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY

Reference
1. http://bwrc.eecs.berkeley.edu/Classes/IcBook/SPICE/

SPICE IMPORT AND EXPORT | 75

76 | CHAPTER 2: MODELING WITH ELECTROCHEMISTRY
 3

Battery Interfaces

This chapter describes the physics interfaces found under the

Electrochemistry>Battery Interfaces branch ( ).

In this chapter:

• The Lithium-Ion Battery Interface

• Lithium-Ion Battery, Deformed Geometry Model Wizard Entry
• The Battery with Binary Electrolyte Interface
• The Lead–Acid Battery Interface
• The Single Particle Battery Interface
• The Lumped Battery Interface
• The Battery Equivalent Circuit Model Wizard Entry
• The Battery Pack Interface
• Shared Nodes for Battery Interfaces
• Theory for the Lithium-Ion Battery Interface
• Theory for the Battery with Binary Electrolyte Interface
• Theory for the Lead–Acid Battery Interface
• Theory for the Single Particle Battery Interface

77
 • Theory for the Lumped Battery Interface
• Theory for the Battery Pack Interface

78 | CHAPTER 3: BATTERY INTERFACES

The Lithium-Ion Battery Interface
The Lithium-Ion Battery (liion) interface ( ), found under the
Electrochemistry>Battery Interfaces branch ( ) when adding a physics interface, is
used to compute the potential and current distributions in a lithium-ion battery.
Multiple intercalating electrode materials can be used, and voltage losses due to
solid-electrolyte-interface (SEI) layers are also included.

The physics interface is based on the works of Newman and others. Ohm’s law is used
to describe the charge transport in the electrodes. For the electrolyte, concentrated
electrolyte theory for a quiescent aprotic (1:1) electrolyte is used to describe charge
and mass transport in the electrolyte phase.

Alternatively, a single-ion conductor charge balance, used by default by the Lithium-Ion

Battery, Single-Ion Conductor (liion) ( ) entry in the model wizard, may be used for
the electrolyte. This option is typically applicable to solid electrolytes.

An extra dimension is included in the porous electrode domains to describe the

transport of solid lithium in the solid electrode phase using Fick’s law.

Dependent Variables and Extra Dimensions

Different combinations of four dependent variables are valid and solved in different
domains. The four dependent variables are:

• φ l, electrolyte potential,
• φ s, electric potential in the electrodes,
• cl, salt concentration in the electrolyte, and
• cs, solid lithium concentration in the electrode particles in the Porous Electrode and
Additional Porous Electrode Material nodes.

The cl variable is not solved for when using the single-ion conductor charge balance
model.

The cs variable is solved for in an extra dimension, using an internal discretization in

the particle dimension, not visible in the ordinary model geometry. The cs dependent
variable, named liion.cs_xxx (where xxx is the tag of the Porous Electrode node,
for instance pce1), can be used to set for instance concentration varying diffusion
coefficients in the particle. The spatial variable of the particle is named xs_xxx_pin1
(for instance, xs_pce1_pin1).

THE LITHIUM-ION BATTERY INTERFACE | 79

 The concentration variation along the extra dimension, at a given position in the real
dimension, can be accessed using the atxd1, atxd2, and atxd3 operators. See also
Using Extra Dimensions and Plotting Results in Extra Dimensions in the COMSOL
Multiphysics Reference Manual.

The surface, center and average values of cs can also be evaluated in the real dimension
by the variable names liion.cs_surface, liion.cs_center, and
liion.cs_average, respectively.

Default Nodes
When this physics interface is added, these default nodes are also added to the Model
Builder — Electrolyte, Insulation, and Initial Values. Then, from the Physics toolbar, add
other nodes that implement, for example, Porous Electrodes and nonporous Electrodes,
and boundary conditions. You can also right-click Lithium-Ion Battery to select physics
features from the context menu.

All nodes are described in Shared Nodes for Battery 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 liion.

DOMAIN SELECTION

Exclude domains that do not conduct current.

OUT-OF-PLANE THICKNESS
See Out-of-Plane Thickness.

80 | CHAPTER 3: BATTERY INTERFACES

CROSS-SECTIONAL AREA
See Cross-Sectional Area.

CHARGE BALANCE MODEL

The Binary 1:1 liquid electrolyte option uses concentrated electrolyte theory to solve
for the lithium salt concentration and the potential as dependent variables in the
electrolyte phase. The option applicable to liquid (or plasticized) organic solvent-based
lithium salt electrolytes.

The Single-ion conductor solves for the electrolyte potential by assuming that all charge
in the electrolyte phase is carried by the positive lithium ions only, so that the
concentration of lithium ions in the electrolyte can be assumed to be constant. The
option is typically applicable to solid phase electrolytes, or electrolytes where the
electrolyte conductivity is not changing as a result of the ion transport in the cell. Since
the electrolyte concentration is not solved for, the single-ion conductor option reduces
the computational load and complexity.

Note that the single-ion conductor option will disable all settings in domain and
boundary nodes applicable to the electrolyte concentration dependent variable.

TRANSPORT MECHANISMS
Convection can be added as an additional transport mechanism. By default, the check
box Convection is not selected. Select the check box to enable convective transport.

Note that this section is not applicable if the Single-ion conductor option is selected in
the Charge Balance Model section.

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.

THE LITHIUM-ION BATTERY INTERFACE | 81

 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. These sections are applicable only
if Convection is selected in the Transport Mechanisms section. There are two consistent
stabilization methods available and selected by default — Streamline diffusion and
Crosswind diffusion. There is one inconsistent stabilization method, Isotropic diffusion,
which is not selected by default.

DEPENDENT VARIABLES
This physics interface defines the following dependent variables (fields): the electrolyte
potential, the electrolyte salt concentration, and the electric potential. The names can
be changed but the names of fields and dependent variables must be unique within a
model.

The electrolyte salt concentration variable is not solved for when using the Single-ion
conductor charge balance model (see previous section).

Certain nodes may add additional dependent variables to the model. For example the
intercalated solid lithium concentration in the Porous Electrode and Additional
Porous Electrode Material nodes.

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.

• Introduction to Electrochemistry Modeling

• About the Domain, Boundary, Edge, Point, and Pair Nodes for the
Lithium-Ion Battery Interface
• Shared Nodes for Battery Interfaces
• Shared Physics Features in the Current Distribution Interfaces
• Theory for the Lithium-Ion Battery Interface

82 | CHAPTER 3: BATTERY INTERFACES

 • Tutorial of a Lithium-Ion Battery: Application Library path
Battery_Design_Module/Batteries,_Lithium-Ion/li_battery_tutorial_2d
• 1D Isothermal Lithium-Ion Battery: Application Library path
Battery_Design_Module/Batteries,_Lithium-Ion/li_battery_1d
• Capacity Fade of a Lithium-Ion Battery: Application Library path
Battery_Design_Module/Batteries,_Lithium-Ion/capacity_fade

About the Domain, Boundary, Edge, Point, and Pair Nodes for the
Lithium-Ion Battery Interface
The Initial Values node and Electrode Reaction are described below, the other nodes
for The Lithium-Ion Battery Interface are described in Shared Nodes for Battery
Interfaces.

Physics nodes are available from the Physics ribbon toolbar (Windows users), Physics
context menu (macOS or Linux users), or right-click to access the context menu (all
users).

Initial Values
The Initial Values node sets the initial values for the electrolyte potential, the electric
potential, and the electrolyte salt concentration.

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 default initial Electrolyte salt concentration, 1·103 mol/m3, is a typical value for
common lithium-ion battery electrolytes. This input field is not available when using
the Single-ion conductor charge balance model.

THE LITHIUM-ION BATTERY INTERFACE | 83

 Electrode Reaction
A default Electrode Reaction node is added to the Internal Electrode Surface or
Electrode Surface physics nodes. Use the Electrode Reaction feature to define the
electrode kinetics for the charge transfer reaction that occurs between the electrolyte
and a nonporous electrode. Additional subnodes are available from the context menu
(right-click the parent node) or from the Physics toolbar, Attributes menu.

See the Electrode Reaction node in Shared Physics Features in the Current
Distribution Interfaces for a general description of the Equilibrium Potential,
Electrode Kinetics and Stoichiometric Coefficients sections.

ELECTRODE KINETICS
In addition to the kinetics expression types described in the link above, two additional
kinetics expressions are available in the Lithium-Ion Battery interface.

The Lithium metal expression can be used to define a lithium metal deposition/
dissolution reaction.

The Insertion Reaction expression can be used for modeling a heterogeneous porous
electrode — that is, when the individual electrode particles are resolved in the model
and defined on the boundaries to the electrolyte domain.

84 | CHAPTER 3: BATTERY INTERFACES

Lithium-Ion Battery, Deformed
Geometry Model Wizard Entry
The Lithium-Ion Battery, Deformed Geometry ( ) model wizard entry is a predefined
multiphysics interface for time-dependent modeling of deformations that occur as a
result of a deposition/dissolution processes in a lithium-ion battery, for instance
lithium metal dissolution at the negative electrode of a lithium-metal battery.

By choosing the multiphysics interface, a Lithium-Ion Battery Interface interface and a

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

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

• The Lithium-Ion Battery Interface

• The Deformed Geometry Interface in the COMSOL Multiphysics
Reference Manual
• The Multiphysics Branch in the COMSOL Multiphysics Reference
Manual
• Deforming Electrode Surface multiphysics coupling node
• Nondeforming Boundary multiphysics coupling node

Lithium Plating with Deformation: Application Library path

Battery_Design_Module/Batteries,_Lithium-Ion/li_plating_with_deformation

LITHIUM-ION BATTERY, DEFORMED GEOMETRY MODEL WIZARD ENTRY | 85

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

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

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

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

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

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

∂x
⋅ n = v dep, tot (3-1)
∂t

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

Mi ν i, m i loc, m
v dep, tot =  ------
ρi  nm F
- -------------------------- (3-2)
i m

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

The boundary condition is implemented similarly to the Normal Mesh Velocity

boundary node in the Deformed Geometry interface.

Tangential Velocities at the Intersection Between a Depositing and a

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

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

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

86 | CHAPTER 3: BATTERY INTERFACES

the tangential direction of the nondepositing boundary, special conditions apply.
These conditions can be derived expressions by assuming growth or dissolution to
occur only in the normal direction of the depositing boundary by addition or removal
of spherical particles (for example metal atoms), see Figure 3-1 below.

Nondepositing material

Electrolyte

Electrode

Nondepositing material

Figure 3-1: Gray/Black arrows in whole stroke indicate the tangential electrode growth/
dissolution velocities, vt, point, at the three-phase intersections between an electrolyte, a
deposition or dissolution electrode and a nondepositing material. Dashed arrows are the
growth or dissolution velocities, vdep, based on the electrodeposition rate expressions. Note
that the tangential velocities depend on both the angle between the depositing surface and
the nondepositing surface, as well as the direction of the normal velocity.

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

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

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

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

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

(3-4)
Case 2: if v dep n nondep ⋅ n dep < 0 v t, point = v dep ( t nondep ⋅ n dep )

Note that Case 2 above results in a lower velocity in the normal direction of the
depositing surface than the deposition velocity, and that this acts toward forming a π/

LITHIUM-ION BATTERY, DEFORMED GEOMETRY MODEL WIZARD ENTRY | 87

 2 angle between the depositing and the nondepositing boundary, a phenomenon
observed in experiments (Ref. 1).

In the Electrodeposition Interfaces, on shared points (2D) and edges (3D) between a
Nondeforming Boundary and a Deforming Electrode Surface, the velocity of the
depositing boundary is set according to the expressions above.

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

88 | CHAPTER 3: BATTERY INTERFACES

The Battery with Binary Electrolyte
Interface
The Battery with Binary Electrolyte (batbe) interface ( ), found under the
Electrochemistry>Battery Interfaces branch ( ) when adding a physics interface, is
used to compute the potential and current distributions in a generic battery. Multiple
intercalating electrode materials can be used, and voltage losses due to film formation
on the porous electrodes can also be included.

Use this physics interface for modeling batteries with alkaline binary (1:1) electrolytes,
such as NiMH or NiCd batteries.

Ohm’s law is used to describe the charge transport in the electrodes, whereas
concentrated electrolyte theory for an alkaline aqueous (1:1) electrolyte is used to
describe charge and mass transport in the electrolyte phase. An extra dimension can be
included in the porous electrode domains to describe transport of species in the solid
electrode phase using Fick’s law.

Dependent Variables and Extra Dimensions

Different combinations of four dependent variables are valid and solved in different
domains. The four dependent variables are:

• φ l, electrolyte potential
• φ s, electric potential in the electrodes
• cl, salt concentration in the electrolyte,
• cs, intercalation concentration in the electrode particles when using the Porous
Electrode and Additional Porous Electrode Material nodes.

The cs variable is solved for in an extra dimension, using an internal discretization in

the particle dimension, not visible in the ordinary model geometry. The cs variable can
be referred to as batbe.cs_surface, batbe.cs_center, or batbe.cs_average.
The concentration variation along the extra dimension can be plotted along the solid
electrode phase using the comp1.xdim1.atxd2 operator. See also Using Extra
Dimensions and Plotting Results in Extra Dimensions in the COMSOL Multiphysics
Reference Manual.

THE BATTERY WITH BINARY ELECTROLYTE INTERFACE | 89

 Default Nodes
When this physics interface is added, these default nodes are also added to the Model
Builder — Electrolyte, Insulation, No Flux, and Initial Values. Then, from the Physics
toolbar, add other nodes that implement, for example, Porous Electrodes and
nonporous Electrodes, and boundary conditions. You can also right-click Battery with
Binary Electrolyte to select physics features from the context menu.

Except for the Initial Values and Porous Matrix Adsorption/Desorption

Reaction nodes, the other nodes are described in Shared Nodes for
Battery 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 batbe.

DOMAIN SELECTION

Exclude domains that do not conduct current.

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.

90 | CHAPTER 3: BATTERY INTERFACES

CROSS-SECTIONAL AREA

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

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

SPECIES
This section contains some global settings for the electrolyte which are used in the
Insertion Reaction type kinetics in the Porous Electrode Reaction node to calculate the
concentration of water in the electrolyte. The default values correspond to a KOH
electrolyte.

• Electrolyte anion molar mass MAn- (SI unit: kg/mol). The default is 0.017 kg/mol.
• Electrolyte cation molar mass MCat+ (SI unit: kg/mol). The default is 0.0391 kg/
mol.
• Solvent molar mass M0 (SI unit: kg/mol). The default is 0.018 kg/mol.

TRANSPORT MECHANISMS
Convection can be added as an additional transport mechanism. By default, the check
box Convection is not selected. Select the check box to enable convective transport.

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.

THE BATTERY WITH BINARY ELECTROLYTE INTERFACE | 91

 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. These sections are applicable only
if Convection is selected in the Transport Mechanisms section. There are two consistent
stabilization methods available and selected by default — Streamline diffusion and
Crosswind diffusion. There is one inconsistent stabilization method, Isotropic diffusion,
which is not selected by default.

DEPENDENT VARIABLES
This physics interface defines these dependent variables (fields), the Electrolyte
potential, the Electrolyte salt concentration and Electric potential. The name can be
changed but the names of fields and dependent variables must be unique within a
model. The Intercalating species concentration in the electrode particles is another,
hidden, dependent variable. This variable is solved for locally and with an independent
variable for the particle radius.

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.

• Introduction to Electrochemistry Modeling

• Domain, Boundary, Edge, Point, and Pair Nodes for the Battery with
Binary Electrolyte Interface
• Shared Nodes for Battery Interfaces
• Shared Physics Features in the Current Distribution Interfaces
• Theory for the Battery with Binary Electrolyte Interface

1D Isothermal Nickel–Metal Hydride Battery: Application Library path

Battery_Design_Module/Batteries,_General/nimh_battery_1d

92 | CHAPTER 3: BATTERY INTERFACES

Domain, Boundary, Edge, Point, and Pair Nodes for the Battery with
Binary Electrolyte Interface
The Battery with Binary Electrolyte Interface shares most of its domain, boundary,
edge, point, and pair nodes with the other battery interfaces, except for Initial Values
and Porous Matrix Adsorption/Desorption Reaction, see Shared Nodes for Battery
Interfaces.

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. Subnodes are available by clicking the
parent node and selecting it from the Attributes menu.

Initial Values
The Initial Values node sets the initial values for the electrolyte potential, the electric
potential, and the electrolyte salt concentration.

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 default initial Electrolyte salt concentration, 1·103 mol/m3, is a typical order of
magnitude for common concentrated aqueous concentrated electrolytes.

Porous Matrix Adsorption/Desorption Reaction

Use this node to model non-faradaic reactions on the porous electrode particle surface,
for instance hydrogen adsorption/desorption in a NiMH battery.

The Porous Matrix Adsorption/Desorption Reaction can be added as a subnode to a

Porous Electrode parent node.

THE BATTERY WITH BINARY ELECTROLYTE INTERFACE | 93

 Enter values or expressions for the Rate expression k (SI unit: mol/(m2·s)) of the
surface reaction and the stoichiometric Coefficient vs (dimensionless) of the
intercalating species for this reaction. The Active specific surface area av (SI unit: 1/m)
will only have an impact on post precessing of the volumetric source variable (mol/
(m3·s)) of the intercalating species.

94 | CHAPTER 3: BATTERY INTERFACES

The Lead–Acid Battery Interface
The Lead–Acid Battery (leadbat) interface ( ), found under the
Electrochemistry>Battery Interfaces branch ( ) when adding a physics interface, is
used to compute the potential and current distributions in a lead–acid battery.

Ohm’s law is used to describe the charge transport in the electrodes, whereas
concentrated electrolyte theory is used to describe charge and mass transport in the
electrolyte phase. Mass balances for the porosities in the porous electrode domains
account for changes in state-of-charge.

Dependent Variables
Different combinations of four dependent variables are valid and solved in different
domains. The four dependent variables are:

• φ l, electrolyte potential
• φ s, electric potential in the electrodes
+ -
• cl, salt concentration in the electrolyte, here H / SO 4
• ε, porosity (volume fraction of liquid electrolyte) in the Negative Porous Electrode
and Positive Porous Electrode nodes.

A lead–acid cell typically consists of five parts: a positive porous electrode (PbO2), a
reservoir of electrolyte, a porous separator, a negative porous electrode (Pb), and two
electrodes in contact with the positive porous electrode and negative porous electrode,
respectively.

Default Nodes
When this physics interface is added, these default nodes are also added to the Model
Builder — Reservoir, Electric Insulation, No Flux, and Initial Values. Then, from the
Physics toolbar, add other nodes that implement, for example, Porous Electrodes and
nonporous Electrodes, and boundary conditions. You can also right-click Lead–Acid
Battery 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

THE LEAD–ACID BATTERY INTERFACE | 95

 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 leadbat.

DOMAIN SELECTION

Exclude domains that do not conduct current.

OUT-OF-PLANE THICKNESS
See Out-of-Plane Thickness.

CROSS-SECTIONAL AREA
See Cross-Sectional Area.

MODEL SETTINGS
The settings for the Molar volume and Transport number determine how the electrolyte
velocity is calculated in the model. The default settings correspond to a lead–acid
battery using sulfuric acid as electrolyte.

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.

DEPENDENT VARIABLES
This physics interface defines the following dependent variables (fields): Electrolyte
potential, Electrolyte salt concentration, Electric potential, and Porosity. The names can

96 | CHAPTER 3: BATTERY INTERFACES

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

• Introduction to Electrochemistry Modeling

• Domain, Boundary, Edge, Point, and Pair Nodes for the Lead–Acid
Battery Interface
• Shared Nodes for Battery Interfaces
• Theory for the Lead–Acid Battery Interface

Discharge and Self-Discharge of a Lead–Acid Battery: Application

Library path Battery_Design_Module/Batteries,_General/pb_acid_battery_1d

Domain, Boundary, Edge, Point, and Pair Nodes for the Lead–Acid
Battery Interface
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).

The Lead–Acid Battery Interface shares all but a few of its domain, boundary, edge,
point, and pair nodes with the other battery interfaces as described in Shared Nodes
for Battery Interfaces.

These domain (and one boundary) nodes are unique for this physics interface and
described here:

• Initial Values • Reservoir

• Negative Porous Electrode • Separator
• Positive Porous Electrode

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 LEAD–ACID BATTERY INTERFACE | 97

 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.

Reservoir
The Reservoir node defines a current balance and a material balance for the salt, here
+ -
H / SO 4 , in a free electrolyte domain.

Use this node for domains that do not contain electrode nor separator material.

The settings of the Electrolyte conductivity σl (SI unit: S/m) and the Electrolyte salt
diffusivity Dl (SI unit: m2/s) values defines the electrolyte salt transport due to
migration and diffusion.

Also convective transport can be of importance in lead–acid cells. You may set the Mean
surface-averaged velocity expression to use analytical expressions for the velocity, based
on the volume changes and the electrolyte current for either the Negative electrode
main reaction or Positive electrode main reaction, or use User defined for an arbitrary
expression for the Velocity u (SI unit: m/s)

For the domain equations in the electrolyte, see the Theory for the Lead–
Acid Battery Interface.

Initial Values
The Initial Values node sets the initial values for the electrolyte potential, the electric
potential, and the electrolyte salt concentration. Use multiple Initial Values nodes to
specify different initial values in different domains.

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.

98 | CHAPTER 3: BATTERY INTERFACES

The default initial Electrolyte salt concentration, 4900 mol/m3, is a typical value for a
standard lead–acid battery.

The initial value of the Porosity (dimensionless) will set the initial electrode
state-of-charge (SOC) in the Negative Porous Electrode and Positive Porous
Electrode nodes.

Negative Porous Electrode

Use the Negative Porous Electrode node to set up current balances for the electrode and
the pore electrolyte in the lead electrode, a material balance for the salt, and a mass
balance for lead, lead oxide, and lead sulfate, using the porosity variable. In addition,
the feature is also able to define the charge transfer reactions that take place in the lead
electrode.

By addition of Porous Electrode Reaction subnodes, the feature is also able to define
the charge transfer reactions that take place at the interface between the pore
electrolyte and the porous electrode matrix. A Porous Matrix Double Layer
Capacitance and a Porous Matrix Adsorption/Desorption Reaction (for the Battery
with Binary Electrolyte interface), can also be added to the node.

ELECTROLYTE PROPERTIES
See the Reservoir node for the settings of this section.

ELECTRODE PROPERTIES
The Porosity at zero charge ε0 and Porosity when fully charged εmax determines the
capacity of the electrode and defines the soc variable. The Exponent on porosity in
electrode exm defines how the effective transport parameters in the porous media
depends on the porosity.

See the Electrode for more information about the settings of this node.

For the domain equations in the electrolyte, see the Theory for the Lead–
Acid Battery Interface.

Positive Porous Electrode

Use the Positive Porous Electrode node to set up current balances for the electrode and
the pore electrolyte in the lead–oxide electrode, a material balance for the salt, and a

THE LEAD–ACID BATTERY INTERFACE | 99

 mass balance for lead, lead oxide, and lead sulfate, using the porosity variable. In
addition, the feature is also able to define the charge transfer reactions that take place
in the lead–oxide electrode.

See Negative Porous Electrode for all settings.

The difference between the Positive and Negative Porous Electrode nodes are the
default values for some of the parameters, for instance of the Equilibrium Potential of
the Porous Electrode subnode.

Separator
Use a Separator node to define a current balance in the electrolyte and a material
+ -
balance for the salt, here H / SO 4 . Both the material and current balances are
defined for porous media.

The Separator node can be added from the Electrolyte submenu.

The Porosity in separator εsep (dimensionless) and the Exponent on porosity in

electrolyte ex (dimensionless) parameters will define how the effective transport
parameters of the pore electrolyte are calculated.

See also the Reservoir node.

For the domain equations in the electrolyte, see the Theory for the Lead–
Acid Battery Interface.

100 | CHAPTER 3: BATTERY INTERFACES

The Single Particle Battery Interface
The Single Particle Battery (spb) interface ( ), found under the
Electrochemistry>Battery Interfaces branch ( ) offers a simplified (compared to, for
instance, the Lithium-Ion Battery interface) approach to battery modeling. The basic
assumptions used are valid when current distribution effects along the depth of the
porous electrodes are negligible, and when the salt concentration gradients in the
electrolyte do not cause significant changes of the local conductivity of the electrolyte.
The validity of the assumptions and the applicability of the single particle approach
depends on various battery parameters values such as electrode porosities and
thicknesses, and the electrode-electrolyte chemistry, in relation to the current load. As
a rule of thumb, the Single Particle Battery interface is typically applicable to battery
currents up to 1C (currents corresponding to a full charge or discharge in one hour).

Due to the lower computational load of the single particle model, the interface is
suitable for models including extended cycling for, for instance, life-time simulations
and thermal simulations of battery packs.

The Single Particle Battery interface models the charge distribution in a battery using
one separate single particle model each for the positive and negative electrodes of the
battery. The core simplification of the single particle model is to treat the large number
of individual electrode particles as a single particle, assuming that the reaction current
distribution across the porous electrodes is uniform. The single particle formulation
accounts for solid diffusion in the electrode particles and the intercalation reaction
kinetics. The ohmic potential drop in the separator is also included in the model, using
a lumped solution resistance term.

The single particle model is either solved in a global version, where all potential
dependent variables are solved globally, or in a local version (available in 1D, 2D and
3D), where the variables are solved for locally in the same space dimension as the
physics interface. The local version, which renders a significantly higher computational
load, is suitable for modeling nonhomogeneous aging in cells where local differences
in the model parameters (such as temperature) induce localized differences in the
battery cell current density. It could also be used for modeling, for instance, cold start
of a battery pack, where local currents will cause local heating with a positive feedback
when the increased temperature raises the local electrolyte conductivity. Note that the
global and local approach both require fairly low currents for the single particle
approach to be valid, as described above. However, it is possible to set up the

THE SINGLE PARTICLE BATTERY INTERFACE | 101

 electrolyte solution resistance as a function of the applied current in order to provide
a better representation even at higher values of current.

The local model contains both global and local variables. Conversion between local
and global variables are done by integrating over the total cell volume.

• 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 spb.

DOMAIN SELECTION
This section is available in 1D, 2D, and 3D. The domain selection of the interface is
used to calculate the battery volume.

OPERATION MODE
Use the Operation mode setting to specify the load of the battery. Galvanostatic lets you
specify the Applied current (A). Charge-discharge cycling lets you specify the settings that
are required to apply a charge-discharge cycle, including constant current, constant
voltage and rest periods. Potentiostatic allows for specifying the Applied voltage (V) and
Circuit voltage source lets you connect to the Electrical Circuits interface.

BATTERY SETTINGS
You may define the host capacities of the two electrodes (which in term will set the
total capacity of the battery) either by the Cell capacity or the Volume fractions
alternative. The for the cell capacity case, the electrode volume fractions are derived by
setting explicit values for the Battery cell capacity in combination with the Fraction of
hosted capacity excess in negative electrode, which can be used to specify the relation in
size between the two electrodes. The fractional volumes correspond to the relative
thicknesses of the porous electrodes to the total thickness of the battery cell. (The

102 | CHAPTER 3: BATTERY INTERFACES

volume fraction of the actual electrode materials within each electrode is defined in the
Positive Electrode and Negative Electrode nodes.)

Use the Model setting (available in 1D, 2D, and 3D) to switch between a Global or Local
definition of the dependent variables of the model. The difference between the global
and local model is described above.

INITIAL CHARGE DISTRIBUTION

The settings of this section are used to specify the target initial solid concentration
(state-of-charge) of the electrodes that will be solved for when the interface is solved
with a Current Distribution Initialization step in the Study sequence. The initial charge
distribution can then be used as initial conditions for a following Time Dependent
study step in the Study.

Cell state-of-charge sets the concentrations based on the cell capacity and the Initial cell
state of charge (1), Cell voltage sets the concentrations based on the cell capacity, and
the Electrode state-of-charges lets you specify the state-of-charge of each electrode
individually.

The Fraction of cyclable species loss after cell assembly can be used to reduce the amount
of cyclable species in relation to the capacity specified in the Battery settings section.
Use this setting to define irreversible losses of cyclable material, for instance due to
solid-electrolyte-interface (SEI) formation in a lithium-ion battery.

POROUS ELECTRODE REACTION KINETICS

This section is only visible if the Operation mode is set to Galvanostatic.

In certain cases the Butler–Volmer kinetics expression, used to define the electrode
reactions, can be inverted in order to define the electrode overpotential as an analytical
function of the current. The advantage of this is that the potential then does not have
to be solved for explicitly as a dependent variable in the model, and the nonlinearities
associated with the exponential Butler–Volmer expression can be avoided. This
improves computational efficiency significantly. The inverse expression can be used
only when

• the anodic and cathodic transfer coefficients are both equal to 0.5
• only one porous electrode reaction is present per electrode
• no double layer capacitance is present
• the battery is running in Galvanostatic mode

THE SINGLE PARTICLE BATTERY INTERFACE | 103

 Enabling Use simplified lithium insertion reaction kinetics expression for either the
Positive electrode or Negative electrode will disable any Porous Electrode Reaction
subnodes to the corresponding electrode node and replace them with a single Lithium
Insertion Reaction subnode.

BATTERY VOLUME
This setting is available in 0D.

CROSS-SECTIONAL AREA
This setting is available in 1D. The setting is used to calculate the battery volume. See
Cross-Sectional Area.

OUT-OF-PLANE THICKNESS
This setting is available in 2D. The setting is used to calculate the battery volume. See
Out-of-Plane Thickness.

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.

ADVANCED SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box. In this section you can set the
Initial values of some of the dependent variables in the interface. The settings are
normally only needed if the model is solved without an initial Current Distribution
Initialization study step in the Study sequence. Also, you can set the check box Exclude
heat source variable from Jacobian. The check box is selected by default in 3D and is not
selected by default in other space dimensions. Note that this check box is relevant only
when coupling to heat transfer interfaces.

104 | CHAPTER 3: BATTERY INTERFACES

DISCRETIZATION
The section is only available in 1D, 2D, and 3D. The chosen Element order will be used
by the dependent variables when the Model is set to Local.

Single Particle Model of a Lithium-Ion Battery: Application Library

path Battery_Design_Module/Batteries,_Lithium-Ion/
li_battery_single_particle

Model Tree Nodes for the Single Particle Battery Interface

When this physics interface is added, these default nodes are also added to the Model
Builder — Electrolyte and Separator, Positive Electrode, and Negative Electrode. Only
one instance each of these nodes can be present in the interface, so you cannot add
additional instances of these nodes, and they cannot be deleted. The selection of these
nodes are locked to the parent selection of the physics interface.

Electrolyte and Separator

The settings of this node are used to define the lumped electrolyte conductivity and
the cross-sectional area of the single particle model. For the conductivity, you may
either specify user-defined settings or make use of the Materials node and the Battery
Materials library.

The settings of the Model Inputs are used to specify the electrolyte salt concentration
when you use the Materials node to provide the electrolyte conductivity.

The Electrolyte solution resistance setting may either be Based on thickness and
conductivity or User defined. The first option will calculate the lumped electrolyte
resistance based on the Separator thickness (m) and the Electrolyte conductivity (S/m),
Effective conductivity correction (1) and the Electrolyte volume fraction in separator (1).
The Fraction of separator resistance value (1) is used to correct for the fact that the
lumped effective electrolyte thickness is thicker than the separator due to distribution
effects in the porous electrodes. It is typically a value larger than 1.

The Separator thickness setting can also be used in combination with the parameters
below to calculate the cross-sectional area of the separator in the battery, and it may
also be used to compute to lumped solution resistance.

THE SINGLE PARTICLE BATTERY INTERFACE | 105

 The Separator cross-sectional area setting may either be Based on thickness and volume
fraction of User defined. The first option will calculate the area based on the Separator
thickness and the Separator volume fraction in battery (1).

Positive Electrode
The settings of this node are used to define the properties of the positive electrode
material.

Subnodes (one Porous Electrode Reaction is added by default) are used to define the
properties of the electrochemical reactions in the electrode. You may also add
additional Porous Electrode Reaction and Porous Matrix Double Layer Capacitance
subnodes. These subnodes are available by clicking the parent node and selecting it
from the Attributes menu, or by right-clicking the parent node.

If the Use simplified reaction kinetics expression for check boxes for the Positive electrode
has been enabled in the Porous Electrode Reaction Kinetics section on the top-node,
only one single Lithium Insertion Reaction is present, and it cannot be deleted.

ELECTRODE SETTINGS
The Solid volume fraction (1) is used to calculate the electrode surface area of the
electrode. If the battery capacity is defined by Volume fractions on the parent interface
node, this setting will also have an impact on the resulting electrode host capacity.

PARTICLE INTERCALATION
This section handles the settings for the intercalating species in the electrode particles.

For the remaining settings of this section see the Porous Electrode node in the
Lithium-Ion Battery and Battery with Binary Electrolyte interfaces.

Negative Electrode
The settings of this node are used to define the properties of the negative electrode
material. The settings are identical to the Positive Electrode.

Lithium Insertion Reaction

This node is available as a subnode to the Positive Electrode and Negative Electrode
nodes.

106 | CHAPTER 3: BATTERY INTERFACES

The node is only present when the Use simplified lithium insertion reaction kinetics
expression for check boxes for either the Positive electrode or Negative electrode has
been enabled in the Porous Electrode Reaction Kinetics section on the top node.

For the rest of the settings of this node, see the Insertion Reaction.

THE SINGLE PARTICLE BATTERY INTERFACE | 107

 The Lumped Battery Interface
The Lumped Battery (lb) interface ( ), found under the Electrochemistry>Battery
Interfaces branch ( ) offers a simplified (compared to, for instance, the Lithium-Ion
Battery or the Single Particle Battery interface) approach to battery modeling.

Instead of differentiating between the various processes in the negative and positive
electrodes, and the electrolyte, the Lumped Battery interface makes use of a small set
of lumped parameters for adding contributions for the sum of all voltage losses in the
battery, stemming from ohmic resistances and (optionally) charge transfer and/or
diffusion processes. The applicability of the lumped approach depends on various
internal battery parameters such as the combination of electrode and electrolyte
materials, porosities and layer thicknesses, and the electrode-electrolyte chemistry, in
relation to the current load.

Due to the limited set of parameters needed, the interface is suitable when only little
information is available about the internal structure, or chemistry, of a battery. Heat
sources are calculated automatically by the physics interface and can be used together
with a Heat Transfer interface for thermal simulations.

The Lumped Battery interface is based on a similar set of equations as The Single
Particle Battery Interface, with additional simplifications based on the assumption that
the activation and concentration overpotentials can be attributed to one electrode only.

The interface solves for the battery state-of-charge as a dependent variable. If

concentration overpotentials are included in the model and calculated based on
diffusion in an idealized particle, the state-of-charge variable is solved for in an extra
dimension, representing a generalized electrode particle (or electrolyte diffusion layer)
wherein concentration overpotentials occur due to limited mass transport of a reacting
species to the electrode-electrolyte interface, where the charge transfer reaction takes
place.

The lumped model is either solved in a global version, where the soc dependent
variable and diffusion extra dimension are defined globally, or in a local version
(available in 1D, 2D, and 3D), where the variables are solved for locally in the same
space dimension as the physics interface. The local version, which renders a
significantly higher computational load, is suitable for modeling inhomogeneous cells
where local differences in the model parameters (such as temperature dependent
resistances) induce localized differences in the battery cell current density. One
example could be cold start of a battery pack, where local currents will cause local

108 | CHAPTER 3: BATTERY INTERFACES

heating with a positive feedback when the increased temperature raises the local
electrolyte conductivity.

The local model contains both global and local variables. Conversion between local
and global variables are done by integrating over the total cell volume.

• Introduction to Electrochemistry Modeling

Parameter Estimation of a Time-Dependent Lumped Battery Model:

Application Library path Battery_Design_Module/Batteries,_Lithium-Ion/
li_battery_1d

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 lb

DOMAIN SELECTION
This section is available in 1D, 2D and 3D. The domain selection of the interface is
used to calculate the battery volume.

OPERATION MODE
Use the Operation mode setting to specify the load of the battery.

Galvanostatic lets you specify the Applied current (A). This can be used to specify the
battery current load. (The expression may be time-dependent using the character t for
time.). Charge-discharge cycling mode lets you specify the settings that are required to
apply a charge-discharge cycle, including constant current, constant voltage and rest
periods. Potentiostatic allows for specifying the Applied voltage (V) and Power allows
for specifying the Applied power (W). Circuit voltage source lets you connect to the
Electrical Circuits interface.

THE LUMPED BATTERY INTERFACE | 109

 BATTERY SETTINGS
The Initial battery cell capacity (C) specifies the battery capacity.

The Initial cell state-of-charge (1) specifies the state-of-charge of the battery when the
simulation starts.

Use the Model setting (available in 1D, 2D and 3D) to switch between a Global or Local
definition of the dependent variables of the model. The difference between the global
and local model is described above.

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

Use Perturbation amplitude (A) to specify the perturbation on the applied battery
current. This section is applicable only for frequency domain, perturbation studies
using the Galvanostatic operation mode.

BATTERY VOLUME
A battery volume variable is used in order to calculate a battery heat source variable
(lb.Qh, SI-unit: W/m3) from the lumped model. The heat source may typically be
used for thermal simulations in combination with a Heat Transfer interface.

A Battery Volume (m3) setting is available in 0D.

In 1D, the selected domain length, in combination with the Cross-Sectional Area is
used for calculating the volume.

In 2D, the selected domain area, in combination with the Out-of-Plane Thickness is
used for calculating the volume.

In 3D, the battery volume equals the volume of the selected domain.

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

In this section you can set the check box Exclude heat source variable from Jacobian. The
check box is selected by default in 3D and is not selected by default in other space
dimensions. Note that this check box is relevant only when coupling to heat transfer
interfaces. Excluding the heat source from the Jacobian may decrease the computation
time.

110 | CHAPTER 3: BATTERY INTERFACES

Model Tree Nodes for the Lumped Battery Interface
When this physics interface is added, these default nodes are also added to the Model
Builder — Cell Equilibrium Potential and Voltage Losses. Only one instance each of
these nodes can be present in the interface, so you cannot add additional instances of
these nodes, and they cannot be deleted. The selection of these nodes are locked to the
parent selection of the physics interface.

Cell Equilibrium Potential

The settings of this node define the thermodynamics of the battery.

Specify the Open circuit voltage at reference temperature (V) and Temperature derivative
of open circuit voltage (V/K) as a function of state-of-charge, in the corresponding
tables. Linear interpolation between the provided values, as well as linear extrapolation
outside the range of values will be used. Note, the temperature derivative of open
circuit voltage data is used to calculate the temperature dependence of the open circuit
voltage and in the calculation of the reversible (entropic) contribution and heat of
mixing contribution to the total heat source.

Also, set the Reference temperature in this node.

Voltage Losses
The settings of this node define the voltage losses that occur in the battery when a
current is applied.

OHMIC OVERPOTENTIAL
The Ohmic Overpotential varies linearly with the battery current. The value of the Ohmic
overpotential at 1C (V) specifies the value of ohmic voltage loss for a battery current of
1C. The 1C current equals the battery capacity value, set a the interface top node,
divided by 1 h.

ACTIVATION OVERPOTENTIAL
Enable Include activation overpotential to add a voltage loss related to the charge
transfer processes in the battery. A Dimensionless charge exchange current value of 1
corresponds to an activation overpotential of approximately 25 mV for a battery
current of 1C. For higher currents the activation overpotential varies approximately
logarithmically with the current magnitude.

THE LUMPED BATTERY INTERFACE | 111

 Enable Include double layer capacitance to include capacitative charging of the double
layer over which the charge transfer processes occur. These effects typically occur on a
time scale of tens of microseconds, or less.

CONCENTRATION OVERPOTENTIAL
Enable Include concentration overpotential to add a voltage loss related to mass
transport (diffusion) processes in the battery. Two different concentration
overpotential models are available: Particle diffusion and Resistor-Capacitor pair.

For Particle diffusion, the magnitude of the concentration overpotential will depend
both on the Open circuit voltage, specified on the Cell Equilibrium Potential node, and
the cycling history of the battery. The value of the Diffusion time constant is related to
the relaxation time of the battery for reaching steady state at open circuit. Increasing
the value of the diffusion time constant will generally increase the concentration
overpotential.

For the Resistor-Capacitor pair option, the concentration overpotential will depend
both on the RC time constant and the RC potential at 1C parameters. The latter
parameter equals the steady-state overpotential that the RC component will approach
for a 1C constant load. (Note that the Particle diffusion overpotential will never reach
a steady state value for a constant load.)

PARTICLE DISCRETIZATION
This section is only available when Include concentration overpotential is enabled, using
a Particle diffusion model. The section handles the settings for how the extra dimension
used for solving the diffusion equation is defined. For the settings of this section, see
the Particle Intercalation node in the Lithium-Ion Battery and Battery with Binary
Electrolyte interfaces.

Capacity Loss
The settings of this node define the capacity loss that occurs in the battery due to
parasitic reactions.

CAPACITY LOSS
The Loss kinetics can be specified by either using a Built in expression or an User defined
expression. The Built in option calculates a loss current based on a Calendar aging time
constant that defines the rate of the parasitic reactions, and dimensionless aging factors
dependent on Voltage, Current, Aging history, and Temperature, respectively. The loss

112 | CHAPTER 3: BATTERY INTERFACES

current is used to calculate the accumulated capacity loss corresponding to the parasitic
reactions.

All aging factors having the value of 1 would result in a constant capacity fade, starting
from initial time, reaching 0 remaining cell capacity when the time is equal to the
Calendar aging time constant, independent of battery SOC, capacity throughput, aging
history and temperature.

Enable Voltage to specify the Offset potential and Transfer coefficient parameters, that
relate how the rate of the parasitic reactions changes when the battery voltage deviates
from the average open circuit voltage. In many battery systems, it is seen that high
state-of-charge values (typically resulting in high battery voltage) accelerate capacity
loss.

Battery lifetime is closely related to the amount of cycled equivalent full cycles. Enable
Current to specify the Cycling capacity loss factor parameter, which defines the
additional capacity loss induced by cycling. For example, a value of 2·10−4 (with all
other aging factors set to 1) would result in an additional capacity fade of 20% for a
cycled amount corresponding to 1000 cycles of the initial capacity.

Enable Aging history to define a decelerating aging rate. Specify the Decelerating aging
factor that defines how many times the capacity loss rate will have been reduced when
all capacity has been lost.

Enable Temperature to specify the Activation energy and Reference temperature

parameters, in order to calculate a temperature-dependent aging factor defined using
an Arrhenius expression.

The User defined option of Loss kinetics can be used to explicitly specify the Loss current.

Short Circuit

SHORT-CIRCUIT CONDUCTANCE
Use this setting to define the short-circuit scenario inside a lumped battery. Define the
Short-circuit conductance Gshort in S to evaluate short-circuit currents and
corresponding heat source. This node can be used to model self discharge in a lumped
battery, along with other short-circuit scenarios.

THE LUMPED BATTERY INTERFACE | 113

 The Battery Equivalent Circuit Model
Wizard Entry
The Battery Equivalent Circuit model wizard entry can be used to define a battery
model based on an arbitrary number of electrical circuit elements. Models created with
the Battery Equivalent Circuit can typically be used to monitor the state-of-charge and
the voltage response of a battery during a load cycle.

When selecting the Battery Equivalent Circuit in the Model Wizard, this adds an
Electrical Circuit interface to the model, including a number of predefined circuit
elements that are used to define the open circuit voltage, the load current and an
internal resistance. Additional circuit elements such as resistors, capacitors and
inductors may be added by the user.

See also The Electrical Circuit Interface.

Figure 3-2: Circuit elements and corresponding node numbers in the Electrical Circuit
interface added by the Battery Equivalent Circuit entry in the Model Wizard.

An Equivalent Circuit Model for a Nickel–Metal Hydride Battery:

Application Library path Battery_Design_Module/Batteries,_General/
nimh_equivalent_circuit_battery

114 | CHAPTER 3: BATTERY INTERFACES

The Battery Pack Interface
The Battery Pack (bp) interface ( ), found under the Electrochemistry>Battery
Interfaces branch ( ) offers a one-to-may approach for setting up multiple battery
cell models, and for connecting them in a 3D geometry. The interface is typically used
together with a heat transfer interface for modeling of thermal pack management and
thermal runaway propagation problems.

The interface defines two types of domain nodes by default — Batteries and Current
Conductors, which are used to define the active battery cells and the electrical wiring
(current collectors, feeders and busbars etc.) of the pack, respectively. The location of
the interconnects between the batteries and the current conductors are defined by the
Negative Connectors and Positive Connectors boundary nodes, which are always also
present by default.

The battery cell models are defined similarly as for The Lumped Battery Interface. All
battery models defined by a Battery Pack interface share the same parameter settings.
Modeling of packs with cells different individual parameter settings may be
accomplished by coupling multiple separate Battery Pack and/or Lumped Battery
interfaces together.

Individual cell models are defined automatically on disjoint sets of battery domains and
each individual battery current load is set implicitly via potential constraints at the
negative/positive connector boundaries between the battery domains and the current
conductor domains. The load of the complete battery pack is defined by boundary
conditions on the external boundaries to the current conductor domains, which may
be added as subnodes to the Current Conductors node.

The Battery Pack interface also defines a heat source that may be coupled to a Heat
Transfer interface, using the Electrochemical Heating node, for modeling battery
cooling and thermal management. The interface is available in 3D only.

• Introduction to Electrochemistry Modeling

• The Lumped Battery Interface

SETTINGS
The Label is the default physics interface name.

THE BATTERY PACK INTERFACE | 115

 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 bp.

DOMAIN SELECTION

Exclude domains that neither conduct current nor are active battery cells.

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

In this section you can set the check box Exclude heat source variable from Jacobian. The
check box is selected by default. Note that this check box is relevant only when
coupling to heat transfer interfaces. Excluding the heat source from the Jacobian may
decrease the computation time.

Thermal Distribution in a Pack of Cylindrical Batteries: Application

Library path Battery_Design_Module/Thermal_Management/
battery_pack_6s2p

Model Tree Nodes for the Battery Pack Interface

When this physics interface is added, these default nodes are also added to the Model
Builder — Batteries, Current Conductors, Negative Connectors, and Positive
Connectors. Only one instance each of these nodes can be present in the interface, so
you cannot add additional instances of these nodes, and they cannot be deleted.

116 | CHAPTER 3: BATTERY INTERFACES

Batteries
The node defines the individual battery cells the battery pack. One battery cell model
is defined per each disjoint domain group in the geometry selection.
EOCV
Icell ηIR ηact ηconc

Iapp

Ishort

Gshort

Figure 3-3: Circuit diagram depicting the available elements of the individual battery
models, defined for each disjoint domain group by the Batteries node (and child nodes).
The circles on the left and right hand sides represent the positive and negative cell
terminals, respectively. The directions of Icell and Iapp correspond to the situation during
charging.

Two subnodes are also added by default — Cell Equilibrium Potential and Voltage
Losses. Only one instance each of these subnodes can be present in the interface, so
you cannot add additional instances of these subnodes, and they cannot be deleted.
The selection of these subnodes are locked to the selection of the Batteries node.

Additional subnodes such as Thermal Event, Capacity Loss, and Short Circuit can be
also be added. The Capacity Loss subnode is a singleton node and the selection is
locked to the selection of the Batteries node. The Short Circuit subnode is also a
singleton node with a default empty selection, that can be set to any of the domains of
the Batteries node. The settings of the both these subnodes are similar to the nodes in
The Lumped Battery Interface.

BATTERY PACK SETTINGS

The Battery pack capacity (C) specifies the battery pack capacity.

The Initial pack cell state-of-charge (1) specifies the state-of-charge of the battery pack
when the simulation starts.

Thermal Event
The settings of this subnode set up an event-based heat source in a battery pack. The
node is typically used to study cell-to-cell propagation of thermal runaway phenomena,
where the time-dependent heat source triggered by the event stems from exothermic

THE BATTERY PACK INTERFACE | 117

 reactions due to (irreversible) decomposition of the electrolyte and/or electrode
materials. Multiple thermal event nodes may be used to model the effect of heat
sources from different reactions. The selection of this subnode applies by default to the
selection of the Batteries node, but may be altered.

The thermal event is triggered by an Event condition, which could be when either the
maximum or average cell temperature exceeds a corresponding trigger temperature, or
if the simulated time exceeds the explicit time that is specified. The event can only be
triggered once per battery cell. The Heat source after event is to be specified as a
function of time elapsed after triggering of the event, and this can be done using
options of Local table, User defined, or From definitions. After the event has been
triggered, the thermal event heat source is added to the total sum of all heat sources
for the battery cell.

In addition, the event may also induce changes in the ohmic overpotentials (internal
resistance) of the battery cells and/or induce cell short circuits. Add ohmic overpotential
after event can be used to specify Ohmic overpotential at 1C after event (V), and the
specified value will be added to the corresponding value specified in the Voltage Losses
subnode after the event. Add short circuit after event can be used to specify Short circuit
conductance after event (S), and the specified value will add a short circuiting current
after the event in a similar way as the Short Circuit node. If a Short Circuit subnode is
already present, the event-induced short circuit current will be added in parallel.

Current Conductors
The settings of this node define the current conductor domains in a battery pack.
When this node is added, these default subnodes are also added — Initial Values and
Insulation.

ELECTRICAL CONDUCTIVITY
The Electrical conductivity (S/m) specifies the electrical conductivity of the current
conductors or feeders in the battery pack.

All the boundary condition subnodes of this node are similar to those described for the
Current Distribution interfaces. See boundary nodes described in Shared Nodes for
Battery Interfaces.

Initial Values
This subnode sets up the initial value of the Electric Potential (V).

118 | CHAPTER 3: BATTERY INTERFACES

Negative Connectors
The settings of this node define the negative connector boundaries between the
battery domains and current conductor domains of a battery pack.

Positive Connectors
The settings of this node define the positive connector boundaries between the battery
domains and current conductor domains of a battery pack.

THE BATTERY PACK INTERFACE | 119

 Shared Nodes for Battery Interfaces
The Battery with Binary Electrolyte Interface, The Lithium-Ion Battery Interface, and
The Lead–Acid Battery Interface share many domain, boundary, edge, point, and pair
nodes.

The following domain and boundary nodes are described in this section and available
for the interfaces as noted (listed in alphabetical order):

• Additional Porous Electrode • No Flux

Material • Porous Conductive Binder
• Concentration • Porous Electrode
• Electrolyte • Porous Electrode Reaction
• Flux • Positive Electrode Selection
• Initial Cell Charge Distribution • Reaction Source
• Negative Electrode Selection • Separator

120 | CHAPTER 3: BATTERY INTERFACES

These shared nodes are described for the Current Distribution interfaces (listed in
alphabetical order).

• Double Layer Capacitance • Electrode Reaction

• Electric Ground • Electrode Surface
• Electric Potential • Electrolyte Current Source
• Electric Reference Potential • Electrolyte Current Density
• Electrode • Electrolyte Potential
• Electrode Current • Harmonic Perturbation
• Electrode Current Density • Insulation
• Electrode Current Source • Internal Electrode Surface
• Electrode-Electrolyte Boundary • Porous Matrix Double Layer
Interface Capacitance
• Electrode Potential • Reference Electrode
• Electrode Power • 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.

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

The 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.

The Electrolyte conductivity, σl (SI unit: S/m), parameter will define how the current
in the domain depends on the gradient of the potential and the concentration variable,
the Diffusion coefficient (SI unit: m2/s), defines how the flux of ions relates to
concentration gradients, and the Transport number t+ (also called transference

SHARED NODES FOR BATTERY INTERFACES | 121

 number), which by default is set to 0.363 (a typical value for Li-ion batteries), specifies
how much of the charge is carried by the positive ions.

Use the Activity dependence on concentration parameter to modify the ion activity. The
default is 1(dimensionless).

For the Battery with Binary Electrolyte interface, also enter the Solution density ρ
(SI unit: kg/m3) (the electrolyte density). The default is 1.293e3 kg/m3 (A typical
value for a KOH electrolyte).

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.

For the domain equations in the electrolyte, see the Theory for the
Battery with Binary Electrolyte Interface and Theory for the Lithium-Ion
Battery Interface sections.

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

See also the Electrolyte node for more information about some of the settings of this
node.

DISSOLVING-DEPOSITING SPECIES
See the Porous Electrode node for more information about some of the settings of this
node.

Porous Electrode
The Porous Electrode node sets up current balances for a porous electrode matrix and
a pore electrolyte, as well as the mass balance for the pore electrolyte in a domain. The
node may also set up a mass balance of an intercalating species in the electrode
particles. By addition of Porous Electrode Reaction subnodes, the feature is also able
to define the charge transfer reactions that take place at the interface between the pore

122 | CHAPTER 3: BATTERY INTERFACES

electrolyte and the porous electrode matrix. A Porous Matrix Double Layer
Capacitance and a Porous Matrix Adsorption/Desorption Reaction (for the Battery
with Binary Electrolyte interface), can also be added to the node.

Use correction factors to account for the lowered diffusion coefficients in the
electrolyte and the lowered conductivities of the electrode, due to the lower volume
fractions of each phase and the tortuosity of the porous matrix.

See also the Electrolyte and Electrode nodes for more information about the settings
of this node.

ELECTROLYTE PROPERTIES
See the Electrolyte node for more information about the settings of this section.

ELECTRODE PROPERTIES
See the Electrode node for more information about the settings of this section

PARTICLE PROPERTIES
By selecting Intercalating particles, the node adds a mass balance and the corresponding
dependent variables for solving for an intercalating concentration. The settings related
to the intercalation are set on the Particle Intercalation child node.

POROUS MATRIX PROPERTIES

The Electrode volume fraction εs and Electrolyte volume fraction ε1 parameters are used
in the mass balance equations to account for the available volume of each phase, and
also in the Porous Electrode Reaction to calculate the surface area. These parameter
values may also be used by the Effective Transport Parameter Correction (next section).
Similarly, the Electrode tortuosity τs and Electrolyte tortuosity τ1 parameters may also
be used by the Effective Transport Parameter Correction (next section).

EFFECTIVE TRANSPORT PARAMETER CORRECTION

Use the settings of this section to calculate effective transport parameters for the
electrode and the electrolyte if your corresponding parameter values refer to
nonporous media.

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.

SHARED NODES FOR BATTERY INTERFACES | 123

 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) 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
A film resistance is typically used for modeling the build-up of a SEI (solid electrolyte
interface) layer in lithium-ion battery graphite electrodes. See also the Electrode
Surface node.

Particle Intercalation
This node is available as a subnode to the Porous Electrode and Additional Porous
Electrode Material nodes in The Lithium-Ion Battery Interface and The Battery with
Binary Electrolyte Interface interfaces. The node is only visible if Intercalating Particles
has been selected on the parent node.

SPECIES SETTINGS
The Initial species concentration cs,init (SI unit: mol/m3) is used by the solver and can
be used to specify the initial state-of-charge of the electrode.

The Maximum species concentration cs,max (SI unit: mol/m3) defines the maximum
possible concentration of the intercalated concentration. The value is used by Porous
Electrode Reaction when the Kinetic expression type has been set to Lithium Insertion.

124 | CHAPTER 3: BATTERY INTERFACES

PARTICLE TRANSPORT PROPERTIES
The Species concentration transport model specifies the diffusion model for the
intercalating species in the electrode particles.

Fick’s law and Baker-Verbrugge both add an extra dimension, defined on the porous
electrode domain, within which a diffusion equation is applied in order to solve for the
concentration distribution along the depth within a single particle of the electrode.
The transport in the extra dimension is defined by the Intercalation diffusivity Ds
(SI unit: m2/s).

Fick’s law defines the molecular flux of the intercalated species as the product of the
diffusion coefficient and the concentration gradient. The Baker-Verbrugge models adds
a correction to the diffusion coefficient based on the Equilibrium potential, Eeq, of the
intercalation reaction. This potential is defined in the Equilibrium Potential section
below. Generally, the Baker–Verbrugge model is better at capturing state-of-charge
dependent transport rates and staging phenomena, whereas Fick’s law may be
numerically more stable. Note that the parameter values of the diffusivity from the
material library generally have been estimated assuming Fick’s law and may have to be
reduced when switching to Baker–Verbrugge.

Use No spatial gradients to assume a constant concentration along the depth of the
particle. No spatial gradients significantly reduces the computational load of the model.

The geometry in the extra dimension is one-dimensional and is defined by the Particle
type (Spheres (the default), Cylinders, or Flakes) together with the Particle mean
center-surface distance rp.

Use the Minimum and the Maximum electrode state-of-charge, SOCmin (dimensionless)
and SOCmax (dimensionless) to specify a nominal state-of-charge window for the
electrode. These values are used together with the Initial Cell Charge Distribution
node to define an initial cell state of charge.

PARTICLE DISCRETIZATION
This section is not available if No spatial gradients is selected under Particle Transport
Settings.

Use these settings to control the Distribution of the mesh and the Element order of the
extra particle dimension.

The predefined distributions Square or Cubic root sequence create mesh distributions
with a denser mesh toward the particle surface.

SHARED NODES FOR BATTERY INTERFACES | 125

 The Use fast assembly in particle dimension option enables an alternative method for
assembling of the diffusion equation in the particle dimension that may decrease
computation time when the number of mesh elements in the battery cell dimension is
of the same order of magnitude as the number of elements in the particle dimension
(this is typically the case for 1D problems). When the fast assembly option is enabled,
it is not possible to postprocess the solid particle concentration along the particle
dimension, and the diffusion coefficient in the particle cannot vary along the particle
depth. The same equations are solved for regardless of assembly method.

The fast assembly option is not available if Baker-Verbrugge species concentration

transport model is enabled.

HEAT OF MIXING
This section is not available if No spatial gradients is selected under Particle Transport
Settings, or if Use fast assembly in particle dimension is enabled under Particle
Discretization.

Include heat of mixing defines a heat source defined as the gradient of the molar
enthalpy times the molar flux of the intercalating species, integrates it over the particle,
and adds it to the total heat source variable in the domain. The molar enthalpy is based
on the Equilibrium potential of the insertion reaction, defined below.

The heat source is typically used when coupling the battery interface to a heat transfer
interface using the Electrochemical Heating node.

The heat of mixing is usually small in relation the other heat sources in the battery, such
as Joule heating in the electrolyte, or the heat of reactions.

EQUILIBRIUM POTENTIAL
This section defines the Equilibrium potential of the intercalation reaction, Eeq
(SI unit: V), used by the Particle Transport Properties and Heat of Mixing sections, when
applicable.

STRESS AND STRAIN

This section is not available if No spatial gradients or the particle type Flakes is selected
under Particle Transport Settings, or if Use fast assembly in particle dimension is enabled
under Particle Discretization.

When modeling diffusion in the particle you may enable the Calculate stress and strain
check box to compute a number stress and strain related variables in the particle. The
variables are based on the Young’s modulus and Poisson’s ratio values and the relative

126 | CHAPTER 3: BATTERY INTERFACES

volume change of the particle. The relative volume change is typically dependent on
the concentration in the particle.

See also Stress and strain in intercalating particles in the theory chapter below.

Diffusion-Induced Stress in a Lithium-Ion Battery: Application Library

path Battery_Design_Module/Batteries,_Lithium-Ion/
diffusion_induced_stress

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 self discharge or capacity fade problems.

See the Electrode Reaction node in Shared Physics Features in the Current
Distribution Interfaces for a general description of the Equilibrium Potential,
Electrode Kinetics and Stoichiometric Coefficients sections.

ELECTRODE KINETICS
The battery interfaces have some tailor-made kinetic expressions types (see also
Electrode Reaction).

Lithium Insertion
The charge transfer reaction can be described by the reaction at the surface of the
electrode particles with subsequent lithium intercalation. This solves the charge
transfer current density in the particles in combination with the diffusion of the
intercalating species (see the theory section).

The Lithium insertion option is available for the Lithium-Ion Battery interface. The
expression is suitable for any positive or negative intercalation reaction. The Reference
exchange current density i0,ref(T) (SI unit: A/m2) or the Rate constant k (SI unit: m/
s) depends on the electrode material in use and the temperature.

Insertion Reaction
The Insertion reaction option is available for the Battery with Binary Electrolyte
interface. It can be used for both the positive and the negative electrode main reactions

SHARED NODES FOR BATTERY INTERFACES | 127

 of a NiMH battery. The Reference exchange current density io,ref(T) (SI unit: A/m2)
depends on the electrode material in use and the temperature.

Lead–Acid Battery Charge and Lead–Acid Battery Discharge

These options are available for the Lead–Acid Battery interface. The kinetic section is
equal between the Lead–acid battery charge or Lead–acid battery discharge, but the
Active specific surface area equations differ.

ADVANCED INSERTION KINETICS SETTINGS

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

By enabling Extrapolate insertion kinetics using first order kinetics for high and low socs
numerical stability can be improved for solid concentration values close to 0 or the
maximum concentration. The feature is enabled by default. Use the Extrapolation soc
window width to specify how close to 0 or the maximum soc the extrapolated kinetics
expression should be used.

The option is available both for the Lithium Insertion and the Insertion Reaction
kinetics.

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.

When using a Particle-based area the particle radius is taken from the parent node if
using Intercalating particles (Lithium-ion and Battery with Binary Electrolyte
interfaces).

For the Lead–Acid Battery interface the active surface area can also be calculated as a
function of the porosity of the electrodes, which changes during discharge and
recharge as defined by the Maximum active surface area, amax (dimensions L2/L3; that
is, the SI unit is 1/m) and the Morphology number (dimensionless).

Reaction Source
Use the Reaction Source node to define sources or sinks in the mass balance of the salt
in the electrolyte. To display this option, click the Show More Options button ( ) and

128 | CHAPTER 3: BATTERY INTERFACES

select Advanced Physics Options then select Reaction Source from the Additional Sources
submenu.

Additional Porous Electrode Material

Use the Additional Porous Electrode Material node to define an additional porous
electrode material in a porous electrode, for instance to solve for an additional
intercalation concentration in the solid phase of the electrode particles. The feature can
only be applied to domains that contain an active Porous Electrode node. A Porous
Electrode Reaction node is added by default.

You specify the reactions occurring on the additional material, giving rise to fluxes in
and out from the electrode particles, using Porous Electrode Reaction subnodes,
which is available from the context menu (right-click the parent node) or from the
Physics toolbar, Attributes menu. Also add a Porous Matrix Double Layer Capacitance
and, for the Battery with Binary Electrolyte interface, a Porous Matrix Adsorption/
Desorption Reaction subnode.

The current sources and sinks defined in the Additional Porous Electrode Material
subnodes are also used in the Porous Electrode node domain equations that describe
the electrolyte and electrode current balances, and the mass balance for the electrolyte
salt.

This physics node is available for the Lithium-Ion Battery and Battery with Binary
Electrolyte interfaces.

See the Porous Electrode for more information about the settings of this node.

Porous Conductive Binder

Use the Porous Conductive Binder node to define an electrochemically inactive but
electronically conductive porous domains.

Use correction factors to account for the lowered diffusion coefficient and
conductivity in the electrolyte and the lowered conductivities of the electrode, as a
result of the lower volume fractions of each phase, and the tortuosity of the porous
matrix.

You may specify the Non-Faradaic Reactions occurring on the domain as a subnode,
which is available from the context menu (right-click the parent node) or from the
Physics toolbar, Attributes menu. You may also add a Porous Matrix Double Layer

SHARED NODES FOR BATTERY INTERFACES | 129

 Capacitance subnode and, Dissolving-Depositing Species section in the porous
conductive binder.

See also the Electrolyte and Electrode nodes for more information about the settings
of this node.

ELECTROLYTE PROPERTIES
See the Electrolyte node for more information about the settings of this section.

ELECTRODE PROPERTIES
See the Electrode node for more information about the settings of this section

POROUS MATRIX PROPERTIES

The Electrode volume fraction εs and Electrolyte volume fraction ε1 parameters are used
in the mass balance equations to account for the available volume of each phase. These
parameter values may also be used by the Effective Transport Parameter Correction (next
section). Similarly, the Electrode tortuosity τs and Electrolyte tortuosity τ1 parameters
may also be used by the Effective Transport Parameter Correction (next section).

EFFECTIVE TRANSPORT PARAMETER CORRECTION

Use the settings of this section to calculate effective transport parameters for the
electrode and the electrolyte if your corresponding parameter values refer to
nonporous media.

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

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

Dependent variables for the volumetric molar concentration are added for each
dissolving-depositing species.

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 and Subtract volume change from electrolyte

130 | CHAPTER 3: BATTERY INTERFACES

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
A film resistance is typically used for modeling the build-up of a SEI (solid electrolyte
interface) layer in lithium-ion battery graphite electrodes. This might be important for
accounting the changes in electrical conductivity of the electronic phase.

This physics node is available for the Lithium-Ion Battery and Battery with Binary
Electrolyte interfaces.

Concentration
Add the Concentration boundary condition from the Electrolyte submenu to set the
Concentration on boundary of the salt to a given value or expression.

No Flux
A No Flux boundary condition is added by default for all external boundaries to an
electrolyte domain.

Select additional nodes from the Electrolyte submenu overwrite this boundary
condition.

Flux
Add the Flux boundary condition from the Electrolyte submenu to set the Salt
electrolyte inward flux.

The flux of ions will be set in the normal direction to the boundary.

Initial Cell Charge Distribution

Use the Initial Cell Charge Distribution global node to define the initial cell voltage or
cell state-of-charge (SOC) of a battery cell. When used together with a Current
Distribution Initialization study step, the node will solve for the intercalated
concentrations in the Porous Electrode and the Additional Porous Electrode Material
nodes in order to comply with the given initial conditions.

SHARED NODES FOR BATTERY INTERFACES | 131

 The node also offers the possibility to balance the electrodes by calculating the
electrode phase volume fractions.

The node only has an effect on the actual equations solved for when used in a Current
Distribution Initialization study step. SOC and porosity variables will however be
defined for all study steps. For more information on the functionality of this feature,
see Initial Charge Distribution in the Battery Cell.

Use the Negative Electrode Selection and Positive Electrode Selection subnodes to
select what domains of the battery model that correspond to the negative and positive
electrodes, respectively. The node is only available in the Lithium-Ion Battery and
Battery with Binary Electrolyte interfaces.

BATTERY CELL PARAMETERS

Select an Initial battery cell setting — Initial cell voltage (the default) or Initial cell
state-of-charge.

The entered Initial cell voltage Ecell,0 (SI unit: V) needs to be a valid value that can be
physically achieved for the combination of state-of-charge windows and equilibrium
potentials of the active materials of the two electrodes (as defined in the Porous
Electrode and Porous Electrode Reaction node). The default is 3 V.

The Initial cell state-of-charge SOCcell,0 (dimensionless) should range between 0 and
1; 0 representing a fully discharged and 1 a completely charged cell. The default is 0.5.

The Battery cell capacity Qcell,0 (SI unit: C) is physically limited by the maximum
amount of cyclable species in the selected electrode materials (as defined in the Porous
Electrode node), and the model geometry (as defined in the Geometry node). A too
high value in combination with a too small electrodes may result in intercalation
concentrations higher that the maximum concentrations, or electrode porosities
higher than one when defining the cell balancing in the next section.

BATTERY CELL ELECTRODE BALANCING

Electrode balancing optimizes the amount of electrode material in each electrode with
regards to the total capacity of the battery cell, and to ensure that the concentration of
intercalated species in electrode material is maintained within the specified
state-of-charge window during cycling.

The feature computes the electrode volume fraction variable for each of the electrodes,
which may be used when defining the electrode volume fractions in the Porous
Electrode nodes. The electrode balancing does not support models using Additional
Porous Electrode Material nodes.

132 | CHAPTER 3: BATTERY INTERFACES

A geometrically larger electrode domain results in a lower electrode volume fraction,
and an electrode with an active material with a relatively narrow SOC window and a
low maximum concentration results in a high electrode volume fraction, and vice versa.

The Fraction of cyclable species loss after cell assembly fcycl,loss (dimensionless) and
Fraction of hosted capacity excess in the negative electrode fhost,neg,ex (dimensionless)
are properties that strongly impact the charge distribution in many battery cell
chemistries. The default values are 0.08 and 0.20, respectively, and represent a typical
case of a fresh lithium-battery cell with a 20% excess of carbon-based negative
electrode, and where 8% of the cyclable lithium is lost due to irreversible process at cell
assembly and initial “formation” cycling.

To balance the electrodes, enter in the Porous Matrix properties section of the Positive
Porous Electrode nodes either <physics interface name>.epss_neg or
physics interface name>.epss_pos (for example, batbe.epss_neg or
liion.epss_pos) in the Electrode Volume Fraction text field, depending on the porous
electrode being a negative or a positive electrode.

Negative Electrode Selection

Use the Negative Electrode Selection subnode with the Initial Cell Charge Distribution
node to select the Porous Electrode domain that is the negative electrode in the
battery model.

The node is only available in the Lithium-Ion Battery and Battery with Binary
Electrolyte interfaces.

Positive Electrode Selection

Use the Positive Electrode Selection subnode with the Initial Cell Charge Distribution
node to select the Porous Electrode domain that is the positive electrode in the battery
model.

The node is only available in the Lithium-Ion Battery and Battery with Binary
Electrolyte interfaces.

SHARED NODES FOR BATTERY INTERFACES | 133

 Theory for the Lithium-Ion Battery
Interface
The Lithium-Ion Battery Interface defines the current balance in the electrolyte, the
current balances in the electrodes, the mass balance for the lithium salt, and the mass
balance of lithium in lithium-ion batteries.

The electrolyte in the modeled batteries has to be a quiescent binary 1:1 electrolyte,
containing lithium cations (Li+) and anions (An-).

The physics interface solves for five dependent variables:

• φ s, the electric potential,

• φ l, the electrolyte potential,
• Δ φ s,film, the potential losses due to a resistive film on the electrode particles in the
porous electrodes, also called solid-electrolyte interface (SEI),
• cs, the concentration of lithium (LiΘs) in the electrode particles, and
• cl, the electrolyte salt concentration.

In the electrolyte and pore electrolyte, two variables are defined, φ l and cl. Assuming
electroneutrality, cl denotes both the Li+ concentration and the An- concentration.

The domain equations in the electrolyte are the conservation of current and the mass
balance for the salt according to the following:

2σ l RT ∂ ln f
∇ ⋅  – σ l ∇φ l + ------------------  1 + -------------- ( 1 – t + )∇ ln c l = i tot + Q l
 F  ∂ ln c l 
∂c l i tot + Q l
ε l ------- + ∇ ⋅ ( – ε l D l ∇c l ) = R l –  --------------------- t +
∂t  F 

where σl denotes the electrolyte conductivity, f the activity coefficient for the salt, t+
the transport number for Li+ (also called transference number), itot the sum of all
electrochemical current sources, and Ql denotes an arbitrary electrolyte current source.
In the mass balance for the salt, εl denotes the electrolyte volume fraction, Dl the
electrolyte salt diffusivity, and Rl the total Li+ source term in the electrolyte.

In the electrode, the current density, is, is defined as

134 | CHAPTER 3: BATTERY INTERFACES

 i s = – σ s ∇φ s

where σs is the electrical conductivity.

The domain equation for the electrode is the conservation of current expressed as

∇ ⋅ i s = – i tot + Q s

where Qs is an arbitrary current source term.

The electrochemical reactions in the physics interface are assumed to be insertion

reactions occurring at the surface of small solid spherical particles of radius rp in the
electrodes. The insertion reaction is described as

+ -
Li + e + Θ s ⇔ LiΘ s

where Θs denotes a free reaction site and LiΘs an occupied reaction site at the solid
particle surface.

The concentration of Θs does not have to be solved for since the total concentration
of reaction sites, cs,max, is assumed to be constant, implying that

c Θs = c s, max – c s

An important parameter for lithium insertion electrodes is the state-of-charge variable

for the solid particles, denoted soc. This is defined as

cs
soc = ----------------
c s, max

The equilibrium potentials E0 of lithium insertion electrode reactions are typically

functions of soc.

The electrode reaction occurs on the particle surface and lithium diffuses to and from
the surface in the particles. The mass balance of Li in the particles is described using

∂c
-------s- + ∇ ⋅ N s = 0
∂t

where, for Fick’s law, the molar flux Ns is defined as

N s = – D s ∇c s

THEORY FOR THE LITHIUM-ION BATTERY INTERFACE | 135

 where cs is the concentration of Li in the solid phase. This equation is solved locally by
this physics interface in a 1D pseudo dimension, with the solid phase concentrations at
the nodal points for the element discretization of the particle as the independent
variables. The gradient is calculated in Cartesian, cylindrical, or spherical coordinates,
depending on if the particles are assumed to be best described as flakes, rods or spheres,
respectively.

For the case of Baker–Verbrugge diffusion (Ref. 3), the flux vector is defined as

∂ ln γ s
N s = –  1 + --------------- D s ∇c s
 ∂ ln x s

where

∂ ln γ s F c s, max – c s ∂E eq
1 + --------------- = – --------  --------------------------- c s ------------
∂ ln x s RT  c s, max  ∂c s

The boundary conditions are defined as follows:

Ns = 0
r=0
N s = – R LiΘ
r = rp

where RLiΘ denotes the molar flux of lithium at the particle surface, caused by the
electrochemical insertion reactions.

The stoichiometric notations used in the physics interface are according to the general
electrochemical reaction as expressed below:

 νox Sox + ne  νred Sred

-
⇔
ox red

where the stoichiometric coefficients, νi, is positive (νox) for products and negative
(νred) for reactants in a reduction reaction. From this definition, the number of
electrons, n, in the electrode reaction can be calculated according to

n = –  zi νi
i

where zi denotes the charge of species i. According to these relations, the lithium
insertion reaction has the following stoichiometric coefficients:

136 | CHAPTER 3: BATTERY INTERFACES

 ν Li+ = – 1
ν An - = 0
ν LiΘs = 1

with a resulting n = 1. These are the default settings for the reactions in this physics
interface. When modeling other reactions, such as irreversible anion oxidation or
noninsertion solid lithium metal deposition, other coefficients have to be used.

In the porous electrodes, itot, denotes the sum of all charge transfer current density
contributions according to:

i tot =  Av,m iloc, m

where, Av denotes the specific surface. The source term in the mass balance is
calculated from:

ν Li+, m i loc, m
R l, p = –  Av,m -------------------------------
nm F
m

It is also possible to specify additional reaction sources, Rl, src, that contribute to the
total species source according to:

R l = R l, p + R l, src

At the surface of the solid particles the following equation applies:

ν LiΘ, m i loc, m A v,m

R LiΘ = –  ---------------------------------
nm F
-------------------------------------
( N shape ε s ) ⁄ r p
m

where the last factor (normally equal to 1) is a scaling factor accounting for differences
between the surface area (Av,m) used to calculate the volumetric current density, and
the surface area of the particles in the solid lithium diffusion model. Nshape is 1 for
Cartesian, 2 for cylindrical, and 3 for spherical coordinates.

If the solid phase diffusion coefficient is very large or if the spatial concentration
gradients in the particle can be neglected, the solid phase concentration evolution in
time can be calculated from

∂ε s c s
------------- = R vΘ
∂t

THEORY FOR THE LITHIUM-ION BATTERY INTERFACE | 137

 The molar source RvΘ at the positive and negative electrodes is given as follows:

ν LiΘ, m A v,m i loc, m

R vΘ = –  -----------------------------------------------
nm F
-
m

A resistive film (also called solid-electrolyte interface, SEI) might form on the solid
particles resulting in additional potential losses in the electrodes. To model a film
resistance, an extra solution variable for the potential variation over the film, Δ φ s, film,
is introduced in the physics interface. The governing equation is then according to

Δφ s, film = i tot R film

where Rfilm (SI unit: Ω·m2) denotes a generalized film resistance. The activation
overpotentials, ηm, for all electrode reactions in the electrode then receives an extra
potential contribution, which yields

η m = φ s – Δφ s, film – φ l – E eq, m

INITIAL CHARGE DISTRIBUTION IN THE BATTERY CELL

The number of parameters in battery models are many, but especially setting the
charge distribution in the cell (that is, the intercalating species concentration in each
electrode material) is not always straightforward because it often requires more
detailed information than just cell voltage and capacity.

It is, however, possible to compute the initial charge distribution taking into account
that initially, when no current is applied on a battery cell and no sources of polarization
apply, it is only the difference between the positive and negative electrode material
equilibrium potentials that dictates the cell voltage. Two constraints can be set up with
the battery cell capacity and voltage as inputs for this computation:

• The battery cell capacity, Qcell,0 (SI unit: C), is equal to the sum of the charge of
cyclable species, Qcycl, in the positive and negative electrodes (and additional porous
electrode materials if present in the model):
Q cell,0 = Q cycl,pos + Q cycl,neg + Q cycl,addm

The cyclable species charge in an electrode, or an additional electrode material, is

defined as:

138 | CHAPTER 3: BATTERY INTERFACES

 Q cycl,electrode = c s,avg,cycl,electrode  Fε s dΩ
Ω electrode

where εs denotes the electrode volume fraction and cs,avg,cycl,electrode is the local
average cyclable species concentration defined as:
c s,avg,cycl,electrode = c s,avg,electrode – soc min c s, max

cs,avg is the average species concentration, which initially, when no concentration

gradients are present within the electrode particles, is equal to the concentration at
the surface of the electrode particles, cs,surf. socmin is the minimum allowed
state-of-charge in the electrode material. The amount of cyclable species charge of
additional electrode materials is calculated similarly.
• The electrode potential is constant in each electrode and the difference between the
positive and negative electrode potentials is equal to cell voltage:

 φ s dΩ  φ s dΩ
Ω Ω
E cell,0 = ---------------------
pos
- – ----------------------
neg

 dΩ  dΩ
Ω pos Ω neg

Initially, when no polarization is present in the cell, the expression is equal to

difference in the open-circuit potential of the electrode materials, Eeq:
E cell, 0 = E eq,pos ( soc pos, 0 ) – E eq,neg ( soc neg, 0 )

The cell voltage is restricted to the open-circuit potential of the electrode materials
and the cell voltage should be set within the following range:
E eq,pos ( soc max ) – E eq,neg ( soc min ) ≤ E cell,0 ≤ E eq,pos ( soc min ) – E eq,neg ( soc max )

where the subscripts max and min of the electrode state-of-charge indicate the
maximum and minimum allowed amount of intercalated species in terms of
state-of-charge in the electrode materials.
For any additional electrode material, the intercalated concentration is constrained
to fulfill
E eq,addm ( soc addm, 0 ) = φ s – φ l

THEORY FOR THE LITHIUM-ION BATTERY INTERFACE | 139

 Alternatively, the potential constraints can be replaced to instead constrain the initial
cell state-of-charge:

• The cell state-of-charge, soccell,0 (dimensionless), relates the battery cell capacity to
the charge of cyclable species in each electrode:
Q cycl,neg + Q cycl,addm,neg = Q cell,0 soc cell,0

Q cycl,pos + Q cycl,addm,pos = Q cell,0 ( 1 – soc cell,0 )

The cell state-of-charge ranges between 0 and 1. A state-of-charge of 0 indicates

that the cell is completely discharged and if it is 1 the cell is fully charged.

BALANCING THE ELECTRODES

The balancing of the electrodes in the cell means that the amount of electrode active
material in each electrode is designed after the battery cell capacity. In other words, the
cyclable species capacity can be fully hosted either in the positive or negative electrode
without having too much unused excess material and to keep the concentration of
intercalating species within the specified state-of-charge window. For batteries this is
of paramount importance to maximize energy density and life-time, and sometimes
also for safety reasons.

The battery interface can supply electrode volume fractions that balance the electrodes.
These are calculated by connecting the amount of active host material — that is, the
maximum amount of cyclable species in the electrode — to the cell capacity initial.
Here, the active host material in the positive electrode is set equal to the cell capacity.
In some battery chemistries, for instance lithium-ion batteries, the host material
amount in both electrodes deviate. Especially, negative carbon-based electrodes are
often set in excess compared to the positive electrode to account for irreversible losses
in the cell during operation. Cyclable species can in some cases be lost directly after cell
assembly. The following relations therefore apply:

Q cell,0
Q host,pos,0 = -----------------------------
1 – f cycl,loss

Q host,neg,0 = ( 1 + f host,neg,ex )Q host,pos,0

where Qhost (SI unit: C) is the amount of active host material, fcycl,loss the fractional
loss of cyclable species, and fhost,neg,ex the fractional excess of negative active host
material.

140 | CHAPTER 3: BATTERY INTERFACES

To calculate the electrode volume fraction, the fact that the amount of active host
material can be computed from the following equation needs to be considered:

Q host =  Δsocc s, max Fε s dΩ

Ω electrode

where Δsoc is the allowed state-of-charge window of the electrode material.

The expression for the electrode volume fraction in each electrode is therefore:

Q host,electrode,0
ε s = ----------------------------------------------------------
 Δsocc s, max FdΩ
Ω electrode

From the electrode volume fraction it is shown that the battery cell capacity should be
selected carefully, because the capacity is limited by the electrode material and size. The
capacity should never be set so that the electrode volume fraction is larger than 1.

Note that electrode balancing described as above does not take into account additional
electrode materials.

STRESS AND STRAIN IN INTERCALATING PARTICLES

The electrode host material can undergo significant volume changes during charging
and discharging. If concentration gradients are present in the electrode particles,
resulting in inhomogeneous elastic deformation, this will give rise to stresses.

Since atomic diffusion in solids is a much slower process than elastic deformation,
mechanical equilibrium is established much faster than that of diffusion. Hence,
mechanical equilibrium can be treated as a static equilibrium problem. In the analysis
below, the electrode particles (spheres or cylinders) are assumed to be isotropic linear
elastic solids.

The relative change in volume δV/V0 is typically dependent on the solid phase
concentration cs (or the state-of-charge variable soc). Note that cs is solved for in a 1D
extra dimension using spherical or cylindrical coordinate systems (for spheres or
cylinders, respectively), as described above. In the equations presented below, the
relative volume change is considered to be a generic function of the concentration ΔV/
V0 = fvol(cs(r)).

THEORY FOR THE LITHIUM-ION BATTERY INTERFACE | 141

 Particle Type: Spheres
The relationships between stress, σ(r) (SI unit: Pa), and strain, ε(r) (SI unit: 1),
expressed in the spherical coordinate system for the radial and tangential components
(considering that σ θ ( r ) = σ φ ( r ) ) are

1 1
ε r ( r ) = ---- [ σ r ( r ) – 2νσ θ ( r ) ] + --- f vol ( c s ( r ) )
E 3

1 1
ε θ ( r ) = ---- [ σ θ ( r ) – ν ( σ θ ( r ) + σ r ( r ) ) ] + --- f vol ( c s ( r ) )
E 3

where E (SI unit: Pa) is Young’s modulus and ν (SI unit:1) is Poisson’s ratio. It is
assumed that these elastic properties are independent of concentration.

The expressions for radial and tangential stresses in a spherical particle of radius rp that
satisfy the boundary condition σr(rp) = 0 and remain finite at r = 0, can be obtained as
follows, by solving the equation for static mechanical equilibrium in the absence of any
body force:

r r
 p 
σ r ( r ) = ---------------------  ----3- f vol ( c s ( r′ ) )r′ dr′ – ----3- f vol ( c s ( r′ ) )r′ dr′
2E 1 1
 
2 2
3(1 – υ) r r

 p0 0 

r r
 p 
σ θ ( r ) = ---------------------  ----3- f vol ( c s ( r′ ) )r′ dr′ + ----3- f vol ( c s ( r′ ) )r′ dr′ – f vol ( c s ( r ) )
E 2 1
 
2 2
3(1 – υ) r r
 p0 0 

where the two integrals represent contributions, respectively, one given by an integral
over the entire volume of the spherical particle and another given by an integral over
a spherical volume of radius r within the particle. Note, that the tangential component
additionally contains a local term as given by the last term in the expression.

The hydrostatic stress σh(r) (SI unit: Pa) (or the mean stress) is given by

σ r ( r ) + 2σ θ ( r )
σ h ( r ) = --------------------------------------
3

The von Mises stress σv(r) (SI unit: Pa) given by

σv ( r ) = σr ( r ) – σθ ( r )

Because of spherical symmetry, one principal shear stress is zero and the other two are
both equal to ( σ r ( r ) – σ θ ( r ) ) ⁄ 2 .

142 | CHAPTER 3: BATTERY INTERFACES

The strain energy density Ws(r) (SI unit: J/m3) accumulated as a result of the elastic
deformation for the isotropically deformed sphere is given as

2 2
σ r ( r ) + 2σ θ ( r ) – 2νσ θ ( r ) ( 2σ r ( r ) + σ θ ( r ) )
W s ( r ) = -------------------------------------------------------------------------------------------------------------
2E

The total elastic strain energy density stored in the host electrode material Ws,tot(r) (SI
unit: J/m3), which provides the driving force for fracture, is obtained as,

rp
3ε s
W s,tot ( r ) = -------
rp
3 
- W s ( r′ )r′ 2 dr′
0

where εs is the electrode volume fraction in the host material.

Particle Type: Cylinders

The relationships between stress, σ(r), and strain, ε(r), expressed in the cylindrical
coordinate system for the radial, tangential and axial components are as follows:

1 1
ε r ( r ) = ---- [ σ r ( r ) – ν ( σ θ ( r ) + σ z ( r ) ) ] + --- f vol ( c s ( r ) )
E 3

1 1
ε θ ( r ) = ---- [ σ θ ( r ) – ν ( σ z ( r ) + σ r ( r ) ) ] + --- f vol ( c s ( r ) )
E 3

1 1
ε z ( r ) = ---- [ σ z ( r ) – ν ( σ r ( r ) + σ θ ( r ) ) ] + --- f vol ( c s ( r ) )
E 3

The expressions for radial, tangential and axial diffusion-induced stresses for a
transversely isotropic cylindrical particle of radius rp are,

r r
 p 
σ r ( r ) = ---------------------  ----2- f vol ( c s ( r′ ) )r′dr′ – ----2- f vol ( c s ( r′ ) )r′dr′

E 1 1
3(1 – υ) r  r

 p0 0 

r r
 p 
σ θ ( r ) = --------------------- ----2- f vol ( c s ( r′ ) )r′dr′ + ----2- f vol ( c s ( r′ ) )r′dr′ – f vol ( c s ( r ) )

E 1 1
3(1 – υ)  r  r
 
 p0 0 

r
 p 
σ z ( r ) = ---------------------  ----2- f vol ( c s ( r′ ) )r′dr′ – f vol ( c s ( r ) )
E 2
3(1 – υ)  r  
 p0 

THEORY FOR THE LITHIUM-ION BATTERY INTERFACE | 143

 The hydrostatic stress σh(r) is given by,

σr ( r ) + σθ ( r ) + σz ( r )
σ h ( r ) = ------------------------------------------------------
3

The von Mises stress σv(r) is given by

2 2 2
( σr ( r ) – σθ ( r ) ) + ( σθ ( r ) – σz ( r ) ) + ( σz ( r ) – σr ( r ) )
σv ( r ) = -----------------------------------------------------------------------------------------------------------------------------------------
2

The strain energy density Ws(r) accumulated as a result of the elastic deformation for
the isotropically deformed cylinder is given as

2 2 2
σ r ( r ) + σ θ ( r ) + σ z ( r ) – 2ν ( σ r ( r )σ θ ( r ) + σ θ ( r )σ z ( r ) + σ z ( r )σ r ( r ) )
W s ( r ) = ---------------------------------------------------------------------------------------------------------------------------------------------------------------------------
2E

The total elastic strain energy density stored in the host electrode material Ws,tot(r) is
given as

rp
2ε s
W s,tot ( r ) = -------
rp
2
- W s ( r′ )r′dr′

0

References
1. K.E. Thomas, J. Newman, and M. Darling, Mathematical Modeling of Lithium
Batteries, Chapter 12 in Advances in Lithium-Ion Batteries, edited by W.A. van
Schalkwijk and B Scrosati, 2002, Kluwer Academic/Plenum Publishers.

2. M. Doyle and others, J. Electrochem. Soc., vol. 143, p. 1890, 1996.

3. D.R. Baker and M.W. Verbrugge, “Intercalate diffusion in multiphase electrode

materials and application to lithiated graphite,” J. Electrochem. Soc., vol. 159, no. 8,
pp. A1341–A1350, 2012.

144 | CHAPTER 3: BATTERY INTERFACES

Theory for the Battery with Binary
Electrolyte Interface
The Battery with Binary Electrolyte Interface defines the current balance in the
electrolyte, the current balances in the electrodes, the mass balance for a salt, and the
mass balance of an intercalating species such as hydrogen in a nickel–metal hydride
battery.

The electrolyte in the modeled batteries has to be a quiescent alkaline binary 1:1
electrolyte, containing a cation (Cat+) and an anion (An-).

The physics interface solves for five dependent variables:

• φ s, the electric potential,

• φ l, the electrolyte potential
• Δ φ s, film, the potential drop due to a resistive film on the electrode particles in the
porous electrodes
• cs, the concentration of an intercalating species in the electrode particles
• cl, the electrolyte salt concentration

In the electrolyte and pore electrolyte, two variables are defined: φ l and cl. Assuming
electroneutrality, cl denotes both the Cat+ concentration and the An- concentration.

The domain equations in the electrolyte are the conservation of current and the mass
balance for the salt according to the following:

∇ ⋅ i l = i tot + Q l
2σ l RT ∂ ln f cl
i l = – σ l ∇ϕ l – ------------------  1 + --------------  t + + ----- ∇ ln c l
F ∂ ln c l c0
∂ε l c l
-----------
- + ∇ ⋅ Nl = Rl
∂t
il t+
N l = – D l ∇c l + ---------
F

where il denotes the electrolyte current density, σl the electrolyte conductivity, f the
activity coefficient for the salt, t+ the transport number for Cat+ (also called
transference number), itot the sum of all electrochemical current sources, c0 the solvent

THEORY FOR THE BATTERY WITH BINARY ELECTROLYTE INTERFACE | 145

 concentration, and Ql denotes an arbitrary electrolyte current source. In the mass
balance for the salt, Nl denotes the flux of the cation, εl the electrolyte volume fraction,
Dl the electrolyte salt diffusivity, and Rl the total Cat+ source term in the electrolyte.

In the electrode, the current density, is, is defined as

i s = – σ s ∇φ s

where σs is the electrical conductivity.

The domain equation for the electrode is the conservation of current expressed as

∇ ⋅ i s = – i tot + Q s

where Qs is an arbitrary current source term.

Reactions occur on the surface of small solid spherical host particles of radius rp. The
reactions can either be electrochemical or chemical adsorption/desorption reactions
not involving electrons.

The electrochemical reactions involve cations or anions and are written generally as

+ - -
ν Cat+ Cat + ν An- An + ne + ν s Θ s ⇔ ν s SΘ s + X+…

where Θs is a free reaction site and SΘs is an occupied reaction site at the solid particle
surface. Additional product species (X, …) are not handled by this physics interface.

The absorption/desorption chemical reactions that do not involve charged species and
are written generally as:

ν s SΘ s ⇔ ν s Θ s + X+…

with a reaction rate k (SI unit: mol/(s·m2)). The signs νs is here positive, and the
reaction rate is defined as positive for reactions going from left to right.

The concentration of Θs does not have to be solved for because the total concentration
of reaction sites, cs, max, is assumed to be constant, implying that

c Θ s = c s, max – c s

An important parameter for intercalation electrodes is the state-of-charge variable soc

for the solid particles, defined as

146 | CHAPTER 3: BATTERY INTERFACES

 cs
soc = -----------------
c s, max

The equilibrium potentials Eeq of intercalation electrodes reactions are typically

functions of the soc.

The reactions occur on the particle surface only, but the intercalant species can be
transported within the particles by diffusion. Within the particles the mass balance can
be written as

∂c
-------s- = – ∇ ⋅ ( – D s ∇c s )
∂t

where cs is the concentration of the intercalating species. This equation is solved locally
by this physics interface in a 1D extra (pseudo) dimension, using a finite element
discretization with the solid phase concentration as dependent variable. The
divergence and gradient operator in the above equation are be applied using either
spherical, cylindrical or Cartesian coordinates, depending on the particle type (spheres,
cylinders, or flakes).

The boundary conditions are as follows:

∂c
-------s- = 0
∂r r=0
∂c s
– D s -------- = R s, tot
∂r r = rp

where Rs, tot is the total surface molar flux of the intercalating species due to the
electrochemical and chemical reactions.

The stoichiometric notations used in the physics interface are according to the general
electrochemical reaction as expressed below:

 νox Sox + ne  νred Sred

-
⇔
ox red

where the stoichiometric coefficients, νi, are positive (νox) for products and negative
(νred) for reactants in a reduction reaction. From this definition, the number of
electrons, n, in the electrode reaction can be calculated according to

THEORY FOR THE BATTERY WITH BINARY ELECTROLYTE INTERFACE | 147

 n = –  zi νi
i

where zi denotes the charge of species i.

In the porous electrodes, itot denotes the sum of all charge transfer current density
contributions according to:

i tot =  Av,m iloc, m

where Av denotes the specific surface. The source term in the mass balance is calculated
from:

ν Cat +, m i loc, m
R l, p = –  Av,m ----------------------------------
nm F
-
m

It is also possible to specify additional reaction sources, Rl, src, that contribute to the
total species source according to:

R l = R l, p + R l, src

At the surface of the solid particles you have that

ν sΘ, m i loc, m A v,m

R s, electrochem = –  ------------------------------
nm F
- -------------------------------------
( N shape ε s ) ⁄ r p
m

where the last factor (normally equal to 1) is a scaling factor accounting for differences
between the surface area (Av,m) used to calculate the volumetric current density, and
the surface area of the particles in the solid lithium diffusion model. Nshape is 1 for
Cartesian, 2 for cylindrical, and 3 for spherical coordinates.

The surface area is commonly derived from the electrode volume fraction, particle size
and shape according to

N shape ε s
A v, m = -----------------------
rp

If the solid phase diffusion coefficient is very large and/or if the spatial concentration
gradients in the particle can be neglected, the solid phase concentration evolution in
time can be calculated from

148 | CHAPTER 3: BATTERY INTERFACES

 ∂ε s c s
------------- = R v, tot
∂t

The molar source, Rv, tot, due to the electrochemical and chemical reactions at the
positive and negative electrodes is given as follows:

ν sΘ, m A v,m i loc, m

R v, tot = –  --------------------------------------------- –
nm F  νs, m Av,m km
m m

A resistive film (also called solid-electrolyte interface, SEI) might form on the solid
particles resulting in additional potential losses in the electrodes. To model a film
resistance, an extra solution variable for the potential variation over the film, Δ φ s,film,
is introduced in the physics interface. The governing equation is then according to

Δφ s, film = i tot R film

where Rfilm (SI unit: Ω·m2) denotes a generalized film resistance. The activation
overpotentials, ηm, for all electrode reactions in the electrode then receives an extra
potential contribution, which yields

η m = φ s – Δφ s, film – φ l – E eq, m

It is also possible to model an electrode reaction at the interface between an electrolyte

and a solid conductor. Typically a reaction of interest could be

+ -
Cat + e ⇔ Y ( s )

where Y could be some metal deposited on the electrode surface. Because this is not
an insertion reaction, cs is of no relevance at this boundary. The stoichiometric
coefficients for the above reaction are:

ν Cat + = – 1
ν An - = 0

This results in the following boundary condition for the species flux at the electrode -
electrolyte interface

ν Cat+, m i m
n ⋅ Nl = –  --------------------------
nm F
-
m

and the following condition for the currents:

THEORY FOR THE BATTERY WITH BINARY ELECTROLYTE INTERFACE | 149

 i tot =  im
i l ⋅ n = i tot
i s ⋅ n = – i tot

where the normal vector n points into the electrolyte domain.

Initial Charge Distribution in the Battery Cell

The number of parameters in battery models are many, but especially setting the
charge distribution in the cell (that is, the intercalating species concentration in each
electrode material) is not always straightforward because it often requires more
detailed information than just cell voltage and capacity.

It is, however, possible to compute the initial charge distribution taking into account
that initially, when no current is applied on a battery cell and no sources of polarization
apply, it is only the difference between the positive and negative electrode material
equilibrium potentials that dictates the cell voltage. Two constraints can be set up with
the battery cell capacity and voltage as inputs for this computation:

• The battery cell capacity, Qcell,0 (SI unit: C), is equal to the sum of the charge of
cyclable species, Qcycl, in the positive and negative electrodes:
Q cell,0 = Q cycl,pos + Q cycl,neg

The cyclable species charge in an electrode is defined as:

Q cycl,electrode = c s,avg,cycl,electrode  Fε s dΩ
Ω electrode

where εs denotes the electrode volume fraction and cs,avg,cycl,electrode is the local
average cyclable species concentration defined as:
c s,avg,cycl,electrode = c s,avg,electrode – soc min c s, max

cs,avg is the average species concentration, which initially, when no concentration

gradients are present within the electrode particles, is equal to the concentration at
the surface of the electrode particles, cs,surf. socmin is the minimum allowed
state-of-charge in the electrode material.
• The electrode potential is constant in each electrode and the difference between the
positive and negative electrode potentials is equal to cell voltage.

150 | CHAPTER 3: BATTERY INTERFACES

  φ s dΩ  φ s dΩ
Ω
---------------------
- Ω
----------------------
E cell,0 = pos
– neg

 dΩ  dΩ
Ω pos Ω neg

Initially, when no polarization is present in the cell, the expression is equal to

difference in the open-circuit potential of the electrode materials, Eeq:
E cell, 0 = E eq,pos ( soc pos, 0 ) – E eq,neg ( soc neg, 0 )

The cell voltage is restricted to the open-circuit potential of the electrode materials
and the cell voltage should be set within the following range:
E eq,pos ( soc max ) – E eq,neg ( soc min ) ≤ E cell,0 ≤ E eq,pos ( soc min ) – E eq,neg ( soc max )

where the subscripts max and min of the electrode state-of-charge indicate the
maximum and minimum allowed amount of intercalated species in terms of
state-of-charge in the electrode materials.

Alternatively, the second constraint can be replaced with another to allow the initial
cell voltage input to be replaced with initial cell state-of-charge:

• The cell state-of-charge, soccell,0 (dimensionless), relates the battery cell capacity to
the charge of cyclable species in each electrode.
Q cycl,neg = Q cell,0 soc cell,0

Q cycl,pos = Q cell,0 ( 1 – soc cell,0 )

The cell state-of-charge ranges between 0 and 1. A state-of-charge of 0 indicates

that the cell is completely discharged and if it is 1 the cell is fully charged.

Balancing the Electrodes

The balancing of the electrodes in the cell means that the amount of electrode active
material in each electrode is designed after the battery cell capacity. In other words, the
cyclable species capacity can be fully hosted either in the positive or negative electrode
without having too much unused excess material and to keep the concentration of
intercalating species within the specified state-of-charge window. For batteries this is
of paramount importance to maximize energy density and life-time, and sometimes
also for safety reasons.

The battery interface can supply electrode volume fractions that balance the electrodes.
These are calculated by connecting the amount of active host material — that is, the

THEORY FOR THE BATTERY WITH BINARY ELECTROLYTE INTERFACE | 151

 maximum amount of cyclable species in the electrode — to the cell capacity initial.
Here, the active host material in the positive electrode is set equal to the cell capacity.
In some battery chemistries, for instance lithium-ion batteries, the host material
amount in both electrodes deviate. Especially, negative carbon-based electrodes are
often set in excess compared to the positive electrode to account for irreversible losses
in the cell during operation. Cyclable species can in some cases be lost directly after cell
assembly. The following relations therefore apply:

Q cell,0
Q host,pos,0 = -----------------------------
1 – f cycl,loss

Q host,neg,0 = ( 1 + f host,neg,ex )Q host,pos,0

where Qhost (SI unit: C) is the amount of active host material, fcycl,loss the fractional
loss of cyclable species, and fhost,neg,ex the fractional excess of negative active host
material.

To calculate the electrode volume fraction, the fact that the amount of active host
material can be computed from the following equation needs to be considered:

Q host =  Δsocc s, max Fε s dΩ

Ω electrode

where Δsoc is the allowed state-of-charge window of the electrode material.

The expression for the electrode volume fraction in each electrode is therefore:

Q host,electrode,0
ε s = ----------------------------------------------------------
 Δsocc s, max FdΩ
Ω electrode

From the electrode volume fraction it is shown that the battery cell capacity should be
selected carefully, because the capacity is limited by the electrode material and size. The
capacity should never be set so that the electrode volume fraction is larger than 1.

152 | CHAPTER 3: BATTERY INTERFACES

Theory for the Lead–Acid Battery
Interface
The Lead–Acid Battery Interface uses concentrated electrolyte theory to model
electrolyte transport and electrodes of changing porosity in a lead-acid battery. The
physics interface solves for the electrolyte salt concentration, electrode porosities,
electrolyte potential, and electrode potential. The notations for these dependent
variables are the following:

• cl, dissociated salt concentration of electrolyte, here H+/HSO4-,

• ε, porosity (volume fraction of liquid electrolyte) of the porous electrodes,
• φ l, electrolyte potential, and
• φ s, electric potential in the electrodes.

A lead–acid cell typically consists of five parts: a positive porous electrode (PbO2), a
reservoir of electrolyte, a porous separator, a negative porous electrode (Pb), and two
current collectors/feeders in contact with the positive porous electrode and negative
porous electrode, respectively.

In this section:

• The Electrode Reactions Equations

• Electrode Kinetics and Active Available Surface Areas
• Electrode Charge Transport Equations
• Electrolyte Transport Equations

The Electrode Reactions Equations

The main electrode reaction in the positive (PbO2) electrode is

- + -
PbO 2 ( s ) + HSO 4 ( aq ) + 3H ( aq ) + 2e ⇔ PbSO 4 ( s ) + 2H 2 O ( l )

and in the negative (Pb) electrode

- + -
Pb ( s ) + HSO 4 ( aq ) ⇔ PbSO 4 ( s ) + H ( aq ) + 2e

During discharge of the battery the direction of the reactions are from left to right.

THEORY FOR THE LEAD–ACID BATTERY INTERFACE | 153

 Electrode Kinetics and Active Available Surface Areas
The electrode kinetics, described using the Butler–Volmer expression, depends on the
electrolyte concentration according to the following:

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

where i0 denotes the exchange current density (SI unit: A/ m2), γ the reaction order
(dimensionless), αa the anodic charge transfer coefficient (dimensionless), αc the
cathodic charge transfer coefficient (dimensionless). The overpotential, η, is according
to the following equation:

η = φ s – φ l – E eq

During a discharge, the active surface area, av (SI unit: m2/ m3), is calculated using
the equation below:

ε – ε0 ξ
a v = a v, max  -----------------------
 ε max – ε 0

where ζ is a morphology correction parameter (dimensionless). This surface area can

also be used for side-reactions such as oxygen evolution and oxygen reduction and the
non-faradaic double layer currents.

In the charging reactions, PbSO4 is a reactant but also an insulator, reducing the
available active surface area. To account for this effect, the following expression can be
used for the active surface area for the charging reactions:

ε – ε 0 ξ ε max – ε
a v, charge = a v, max  -----------------------  -----------------------
 ε max – ε 0  ε max – ε 0

Electrode Charge Transport Equations

Ohm’s law describes the transport of charge in the electrode’s current collectors and
feeders:

i s = – σ s ∇φ s

In the porous electrode domains the following expression is used:

exm
is = –ε σ s ∇φ s

154 | CHAPTER 3: BATTERY INTERFACES

where ε denote the porosity of the electrode and exm is an empirical parameter that
describes the correction factor for the effective transport properties.

Current conservation is described by ∇ ⋅ i s = Q s . Here Qs is the sum of all current

contributions.

Electrolyte Transport Equations

A modified version of Ohm’s law describes the charge transport in the electrolyte. In
the reservoir, the current density expression is defined as

σ l RT
i l = – σ l ∇φ l +  -------------- ( 1 – 2t + )∇ ln c l
F

where σl denotes the electrolyte conductivity, R the molar gas constant, T the
temperature, F Faraday’s constant, and t+ the transport number.

In the porous domains (the separator and the porous electrodes), it is defined as

ex σ l RT
i l = ε ( – σ l ∇φ l ) + ε  -------------- ( 1 – 2t + )∇ ln c l
ex
 F 

Current conservation is described by ∇ ⋅ i l = Q l . Here Ql denotes the sum of all

current contributions.

The dissociated salt ions can be transported due to convection, migration and
diffusion. The molar flux vector, Nl, (SI unit: mol/(m2·s)), is written as:

N l = – D∇c l + uc l

Where D (SI unit: mol/(s/m2)) is the binary diffusion coefficient into which the
migration effects are incorporated, and u (SI unit: m/s) is the volume averaged
velocity.

In the reservoir, the material balance equation is

∂
c = ∇ ⋅ ( D∇c l ) – u ⋅ ∇c l
∂t l

In the porous electrodes the electrochemical reactions give rise to sources in the
material balance equation, resulting in

∂ ex
ε c = ∇ ⋅ ( ε D∇c l ) – u ⋅ ∇c l + R l
∂t l

THEORY FOR THE LEAD–ACID BATTERY INTERFACE | 155

 where Rl is the a source term (SI unit: mol/s /m3) resulting from the electrochemical
reactions. This source term is according to the equation below:

a v, m i m
Rl = –  ------------------
nm F
- ( ( 1 – c l V e ) ( ( 1 – t + )ν
+
H ,m
+ t + ν HSO , m ) – c l V 0 ν H2O, m )
-
4

where nm denotes the number of electrons involved in reaction (dimensionless), V 0

the partial molar volume of the solvent (H2O) (SI unit: m3/mol), V e the partial molar
volume of the electrolyte (SI unit: m3/mol),

ν H +, m

the stoichiometric coefficients for the proton,

ν HSO - , m
4

the stoichiometric coefficient for the bisulfate ion, and

ν H2O, m

the stoichiometric coefficient for water in reaction m.

In the separator, the corresponding transport equation is used for the electrolyte, but
where the source term, Rl, is zero.

For a boundary, the flux of electrolyte species due to the electrochemical reactions is
calculated according to

im
n ⋅ Nl = –  n-----------
mF
- ( ( 1 – t + )ν+
H ,m
+ t + ν HSO , m )
-
4

As the solid material in the electrodes react, the porosity changes due to volume
changes. This is described by the equation below:

∂ε a v, m i m
∂t
=  ------------------
nm F
- ( ν Pb, m V Pb + ν PbO2, m V PbO2 + ν PbSO4, m V PbSO4 )
m

where V i denotes the molar volumes (SI unit: m3/mol) for the solid materials in the
electrodes,

ν Pb, m

the stoichiometric coefficient of lead,

156 | CHAPTER 3: BATTERY INTERFACES

 ν PbO2, m

the stoichiometric coefficient of lead oxide, and

ν PbSO4, m

the stoichiometric coefficient for lead sulfate in reaction m. For a species with a known
density, ρi (SI unit: kg/m3), and molar mass Mi it can be calculated as

Mi
V i = -------
ρi

In the separator the porosity is constant.

For results and analysis purposes the following state-of-charge expression, soc, for the
electrodes, is also defined

ε – ε0
soc =  -----------------------
 ε max – ε 0

Assuming that the main Pb and PbO2 reactions are the main contributions to the
currents in each electrode, the average superficial velocity in each electrode
compartment can be calculated as

il
u PbO2 = – ------- ( ( V PbSO4 – V PbO2 – ( 3 – 2t + )V e + 2V 0 ) ) )
2F

and

il
u Pb = – ------- ( V Pb – V PbSO4 – ( 1 – 2t + )V e )
2F

Because the reservoir is normally adjacent to the positive PbO2 electrode,

u ≈ u PbO2

is usually a good approximation in the reservoir and

u ≈ u Pb

can be used in the separator.

These assumptions result in a noncontinuous velocity, and hence a noncontinuous

convection contribution to the electrolyte transport, at the interface between the

THEORY FOR THE LEAD–ACID BATTERY INTERFACE | 157

 separator and reservoir domains. The physical background to this is that as water is
either consumed or created at the positive electrode during charge or discharge, the
liquid level in the reservoir either rises or falls. However, the combination of low
velocities and moderate concentration gradients at the separator/reservoir interface
makes these velocity approximations acceptable in most cases.

158 | CHAPTER 3: BATTERY INTERFACES

Theory for the Single Particle
Battery Interface
The Single Particle Battery Interface models the charge distribution in a battery by
accounting for solid diffusion in the electrode particles and the intercalation reaction
kinetics. The ohmic potential drop in the electrolyte is included in the model using a
lumped solution resistance term.

The cell potential Ecell (SI unit: V) is defined as

E cell = φ s, pos – φ s, neg = E pos – E neg + Δφ l

where φ s, pos and φ s, neg are the potentials of the electron conducting phase (one for
each electrode), Epos and Eneg are the electrode potentials, and Δφ l is the potential
drop over the electrolyte phase separating the electrodes.

The battery cell current density, icell (SI unit: A·m−2), is defined as

Δφ l
i cell = ----------
R sol

where Rsol (SI unit: Ω·m2) is the solution resistance.

For the global formulation, the potential drop in the electrolyte solution phase is
obtained by the relation

A sep i cell = I cell

where Asep (SI unit: m2) is the separator cross-sectional area and Icell (SI unit: A) is
the battery cell current.

For the local formulation, the following relation is used

 icell dvol dΩ
Ω
---------------------------------
A sep = I cell
V cell

where Vcell is the cell volume and Ω is the selected domain where the single particle
interface is active. Note that dvol is the cell cross-sectional area in 1D, the
out-of-plane-thickness in 2D and 1D with axial symmetry, and is equal to 1 in 3D and

THEORY FOR THE SINGLE PARTICLE BATTERY INTERFACE | 159

 2D with axial symmetry space dimensions. In 1D with axial symmetry and 2D with
axial symmetry, the expressions computing the volume integrals are also multiplied by
2πr.

The separator area Asep can be calculated from the following relation if the separator
thickness Lsep and the volume fraction εsep occupied by the separator in the battery
are known

ε sep V cell
A sep = ----------------------
L sep

The solution resistance in the separator Rsol,sep can be calculated from the separator
thickness and the effective electrolyte conductivity σl,eff (accounts for separator
porosity correction) as follows,

L sep
R sol,sep = -------------
σ l, eff

To compensate for the contributions to the ohmic resistance from the electrolyte
potential drop in the electrodes, the above can also be multiplied by a fraction number
X, typically greater than 1,

R sol = XR sol,sep

The charge balance for each electrode is as follows for the global case:

 
± I cell = V electrode 
  Av, m iloc, m + Av,dl idl
m

where Velectrode is the porous electrode volume, iloc is the local intercalation current
density, idl is the double layer current density, and Av denotes the active specific surface
area.

For the local formulation, the charge balance is given as,

A sep  
± i cell ----------- = ε electrode 
V cell   Av, m iloc, m + Av,dl idl
m

where εelectrode is the porous electrode volume fraction in the battery.

160 | CHAPTER 3: BATTERY INTERFACES

In the above equations, the +sign applies for the positive electrode and the -sign applies
for the negative electrode. In this interface, charge currents are positive and discharge
currents are negative.

Diffusion in the active material particles in the positive and negative electrodes is
described by Fick’s second law as

∂c
-------s- = – ∇ ⋅ ( – D s ∇c s )
∂t

where cs is the concentration of the intercalating species in the solid phase and Ds is
the solid phase diffusion coefficient. The diffusion equation is solved either globally or
locally (depending on the selection of either global or local formulation, respectively)
by this physics interface in a 1D pseudo extra dimension corresponding to the particle
dimension. The gradient is calculated in Cartesian, cylindrical, or spherical
coordinates, depending on if the particles are assumed to be best described as flakes,
rods or spheres, respectively.

The boundary conditions at the center and surface of the particle are as follows:

∂c
-------s- = 0
∂r r=0
∂c s
– D s -------- = – R sΘ
∂r r = rp

where rp is the radius of the electrode active material particle and RsΘ denotes the
molar flux of the cation at the particle surface, caused by the electrochemical insertion
reactions.

At the surface of the solid particles, the molar flux is coupled to the rate of the lithium
intercalation reaction and the following equation applies:

ν sΘ, m i loc, m A v,m

R sΘ = –  ------------------------------
nm F
- -------------------------------------
( N shape ε s ) ⁄ r p
m

where the last factor (normally equal to 1) is a scaling factor accounting for differences
between the surface area (Av,m) used to calculate the volumetric current density, and
the surface area of the particles in the solid lithium diffusion model. νsΘ denotes the
stoichiometric coefficient of the intercalating species in the electrode particles, nm is
the number of transferred electrons, and εs is the volume fraction of the electrode

THEORY FOR THE SINGLE PARTICLE BATTERY INTERFACE | 161

 phase in the porous electrode. Nshape is 1 for Cartesian, 2 for cylindrical, and 3 for
spherical coordinates.

If the solid phase diffusion coefficient is very large and/or if the spatial concentration
gradients in the particle can be neglected, the solid phase concentration evolution in
time can be calculated from

∂ε s c
------------s- = R vΘ
∂t

The molar source RsΘ at the positive and negative electrodes is given as follows:

ν sΘ, m A v,m i loc, m

R vΘ = –  ----------------------------------------------
nm F
m

BATTERY CELL VOLUME, ELECTRODE HOST CAPACITIES AND VOLUME

FRACTIONS
In 0D the battery cell volume Vcell is specified by the user. In higher dimensions, the
cell volume Vcell, is defined according to

V cell =  dvol dΩ
Ω

where Ω is the selected domain where the single particle interface is active, and dvol is
the cell cross-sectional area in 1D, the out-of-plane-thickness in 2D and 1D with axial
symmetry, and is equal to 1 in 3D and 2D with axial symmetry space dimensions. In
1D with axial symmetry and 2D with axial symmetry, the expressions computing the
volume integrals are also multiplied by 2πr. Note that for some cases, Vcell is explicitly
only needed to calculate the heat source variables.

The porous electrode volume Velectrode is related to the cell volume according to

V electrode = ε electrode V cell

The electrode host capacities are related to the electrode volume fractions. For the
global formulation, the following relation holds for the amount of active host material
Qhost (SI unit: C):

Q host = V electrode ε s Δsocc s, max F

162 | CHAPTER 3: BATTERY INTERFACES

where Δsoc is the allowed state-of-charge window of the electrode material and cs,max
is the maximum concentration of the intercalating species.

For the local formulation, the following relation applies:


Q host = ε electrode ε s Δsocc s, max Fd vol dΩ
Ω

In this interface, the electrode host capacities can be specified by either providing the
amount of cyclable material (cell capacity) and a balancing relation between the two
electrodes, or by explicitly providing the electrode volume fractions in the cell. The
amount of cyclable species is assumed to originate from the positive electrode material.
In some battery chemistries, for instance lithium-ion batteries, the host material
amount in both electrodes deviate. Negative carbon-based electrodes lithium-ion
batteries are for instance often applied in excess compared to the positive electrode in
order to avoid lithium metal plating during high rate charging. Cyclable species can in
some cases be lost directly during the first “formation” cycles after cell assembly due
to parasitic reactions. A typical example is the forming of the SEI layer on the negative
graphite particles in lithium-ion batteries. The following relations therefore apply:

Q cell,0
Q host,pos = -----------------------------
1 – f cycl,loss

Q host,neg = ( 1 + f host,neg,ex )Q host,pos

where fcycl,loss the fractional loss of cyclable species, and fhost,neg,ex the fractional
excess of negative active host material.

INITIAL CHARGE DISTRIBUTION IN THE BATTERY CELL

The initial state of charge of the battery is explicitly determined by the initial
concentration values of the active species in each electrode. These concentration levels
are however not always known a priori. A Current Distribution Initialization study step
may be used to calculate the initial concentration levels of two electrodes based on the
input in the Initial Charge Distribution section. The initial cell state-of-charge, cell
voltage, or the (individual) electrode state-of-charges can be specified.

The battery cell capacity, Qcell,0 (SI unit: C), is equal to the sum of the charge of
cyclable species, Qcycl, in the positive and negative electrodes.

Q cell,0 = Q cycl,pos + Q cycl,neg

THEORY FOR THE SINGLE PARTICLE BATTERY INTERFACE | 163

 The cyclable species charge Qcycl in an electrode is defined as follows, for the global
formulation,

Q cycl = V electrode ε s ( c s,avg – soc min c s, max )F

where cs,avg is the average species concentration, which initially, when no

concentration gradients are present within the electrode particles, is equal to the
concentration at the surface of the electrode particles, cs,surf. socmin is the minimum
allowed state-of-charge in the electrode material.

For the local formulation, the following relation holds:


Q cycl = ε electrode ε s ( c s,avg – soc min c s, max )Fd vol dΩ
Ω

In case of the user input being the initial cell state-of-charge soccell,0, the cyclable
amount of species in each electrode is related to the cell capacity as follows:

Q cycl,neg = Q cell,0 soc cell,0

Q cycl,pos = Q cell,0 ( 1 – soc cell,0 )

The cell state-of-charge ranges between 0 and 1. A state-of-charge of 0 indicates that

the cell is completely discharged and if it is 1 the cell is fully charged.

In case of the user input being the initial cell voltage Ecell,0, the following relation
applies for the global formulation,

E cell,0 = E cell = E pos – E neg + Δφ l

For the local formulation, the following relation holds:

 ((E cell,0 –E pos +E neg

)⁄R )d
sol vol dΩ
Ω
----------------------------------------------------------------------------------------------------
A sep = I cell
V cell

If the individual initial electrode operational state-of-charges (socop,pos,0 and

socop,neg,0) are specified, the following relations apply:

Q cycl,neg = Q host,neg soc op,neg,0

Q cycl,pos = Q host,pos soc op,pos,0

164 | CHAPTER 3: BATTERY INTERFACES

ELECTROCHEMICAL HEAT SOURCES
In order to model the energy balance of an electrochemical cell, a Heat Transfer
interface is used to model the heat transport and the Single Particle Battery interface
is used to generate the heat sources and sinks due to the electrochemical currents.

The expressions for the heat sources in the porous negative/positive electrode (due to
the electrochemical reaction) Qh,electrode (SI unit: W/m3) is as follows:

∂E eq, m
Q h,electrode = ε electrode  Av, m iloc, m  E – Eeq, m + T ------------------
∂T 
-
m

The ohmic heating in the electrolyte phase Qh,sol (SI unit: W/m3) is

Δφ l i cell A sep
Q h,sol = ------------------------------
V cell

The total volumetric cell heat source Qh,cell (SI unit: W/m3) can be written as

Q h,cell = Q h,neg + Q h,pos + Q h,sol

THEORY FOR THE SINGLE PARTICLE BATTERY INTERFACE | 165

 Theory for the Lumped Battery
Interface
The Lumped Battery Interface makes use of a small set of lumped parameters for
adding contributions for the sum of all voltage losses in the battery, stemming from
ohmic resistances and (optionally) change transfer or diffusion processes.

Generally, the battery cell voltage Ecell (SI unit: V) is defined as

E cell = E OCV ( SOC, T ) + η IR + η act + η conc

where ηIR is the ohmic overpotential, ηact is the activation overpotential, and ηconc is
the concentration overpotential. EOCV is the cell open circuit voltage which is
dependent on the state-of-charge SOC and temperature T according to,

∂E OCV ( SOC )
E OCV ( SOC, T ) = E OCV,ref ( SOC ) + ( T – T ref ) ------------------------------------
∂T

where EOCV,ref is the open circuit voltage at a reference temperature Tref.

The time evolution of SOC is defined as

∂SOC- I cell
--------------- = ------------
∂t Q cell

where Icell (SI unit: A) is the applied current and Qcell (SI unit: C) is the battery cell
capacity that is set equal to the initial battery cell capacity Qcell,0 (SI unit: C). The
initial cell state-of-charge is specified by SOCcell,0. If the concentration overpotential
is calculated based on particle diffusion, SOC is replaced by the average
state-of-charge, SOCaverage, in both the above equations.

The lumped voltage loss associated with ohmic process in the electrolyte and
electrodes is given as

I cell
η IR = η IR,1C ----------
I 1C

where ηIR,1C is the ohmic overpotential at 1C, and

166 | CHAPTER 3: BATTERY INTERFACES

 Q cell,0
I 1C = ------------------
3600 s

The lumped voltage loss associated with activation overpotential on both the positive
and negative electrode surfaces is defined as

I cell
η act = ------------ asinh  -------------------
2RT
F  2J 0 I 1C

where R denotes the molar gas constant, T the temperature, F Faraday’s constant, and
J0 the dimensionless charge exchange current.

For fast transients or for frequency domain simulations, it may also be of interest to
include the double layer capacitance between the electrode and electrolyte phases in
the battery. In this case, one cannot derive an analytical expression for the activation
overpotential. Instead, the activation overpotential is solved for as a dependent variable
fulfilling

I cell = I ct + I dl

where Ict is the charge transfer current and Idl is the double layer current. They are
defined as

η act F – η act F
I ct = J 0 I 1C  exp   -------------- – exp  -----------------  
   2RT   2RT   

and

∂η act
I dl = I 1C C dl,1C -------------
∂t

where the normalized 1C double layer capacitance, Cdl,1C, relates the double layer
current to the time derivative of activation potential. Note that the above equation
assumes that the time derivative of the equilibrium potential is orders of magnitude
lower than the time derivative of the activation potential.

Concentration overpotential effects can be modeled either based on diffusion in an

idealized particle or by using an RC pair (a linear resistor coupled in parallel with a
capacitor). In the former case, Fickian diffusion of a dimensionless SOC variable is
solved for in 1D on an interval of length 1 with X as the dimensionless spatial variable
according to

THEORY FOR THE LUMPED BATTERY INTERFACE | 167

 ∂SOC
τ ---------------- = – ∇ ⋅ ( – ∇SOC )
∂t

where τ is the diffusion time constant. The diffusion equation is solved either globally
or locally (depending on the selection of either global or local formulation,
respectively) in a 1D pseudo extra dimension corresponding to the particle dimension.
The gradient is calculated in Cartesian, cylindrical, or spherical coordinates, depending
on if the particles are assumed to be best described as flakes, rods or spheres,
respectively.

The boundary conditions at the center and surface of the particle are as follows:

∇SOC = 0 X=0
τI cell
∇SOC = ------------------------------
N shape Q cell
X=1

where Nshape is 1 for Cartesian, 2 for cylindrical, and 3 for spherical coordinates. The
initial cell state-of-charge is specified by SOCcell,0. The surface state-of-charge,
SOCsurface, is defined at the surface of the particle. The average state-of-charge,
SOCaverage, is defined by integrating over the volume of the particle, appropriately
considering Cartesian, cylindrical, or spherical coordinates. Note that, as mentioned
above, SOCaverage is used in the definition of Ecell.

The lumped voltage loss associated with concentration overpotential is defined as

η conc = E OCV ( SOC surface, T ) – E OCV ( SOC average, T )

For the latter case, where the concentration overpotential calculation is done using an
RC pair, ηconc is defined as

∂η conc
RC ---------------- + η conc = RI cell
∂t

where the RC time constant, τRC = RC, and the RC potential at 1C, ERC,1C = RI1C.

BATTERY CELL VOLUME

In 0D, the battery cell volume Vcell is specified by the user. In higher dimensions, the
cell volume Vcell, is defined according to

V cell =  dvol dΩ
Ω

168 | CHAPTER 3: BATTERY INTERFACES

where Ω is the selected domain where the Lumped Battery interface is active, and dvol
is the cell cross-sectional area in 1D, the out-of-plane-thickness in 2D and 1D with
axial symmetry, and is equal to 1 in 3D and 2D with axial symmetry space dimensions.
In 1D with axial symmetry and 2D with axial symmetry, the expressions computing
the volume integrals are also multiplied by 2πr. Note that for some cases, Vcell is
explicitly only needed to calculate the heat source variables.

ELECTROCHEMICAL HEAT SOURCES

In order to model the energy balance of an electrochemical cell, a Heat Transfer
interface is typically used to model the heat transport and the Lumped Battery
interface is used to generate the heat sources and sinks due to the electrochemical
currents.

The battery heat source (SI unit: W) is defined as follows, if concentration

overpotential is not included:

∂E OCV ( SOC, T )
Q h =  η IR + η act + T ------------------------------------------- I cell
∂T

If concentration overpotential is included and modeled based on diffusion in an

idealized particle, the battery heat source (SI unit: W) is defined as

∂E OCV ( SOC surface, T )

Q h =  η IR + η act + T ----------------------------------------------------------- I cell + Q mix
∂T

where the heat of mixing, Qmix, is defined as

1
N shape Q cell ∂E OCV,therm ∂SOC ∂SOC N – 1
Q mix
τ 
= ------------------------------ -------------------------------- ---------------- ---------------- X shape ∂X
∂SOC ∂X ∂X
0

with the thermoneutral voltage, EOCV,therm, given as

∂E OCV ( SOC )
E OCV,therm = E OCV,ref ( SOC ) – T ref ------------------------------------
∂T

If concentration overpotential is included by using an RC pair, the battery heat source

(SI unit: W) is defined as

∂E OCV ( SOC, T )
Q h =  η IR + η act + T ------------------------------------------- I cell + Q mix
∂T

where Qmix is defined as

THEORY FOR THE LUMPED BATTERY INTERFACE | 169

 2
η conc
Q mix = -------------
R

CAPACITY LOSS
Capacity loss in batteries is a complex process, encompassing a multiple of different
phenomena. Depending on the battery chemistry, the aging mechanisms will be
different.

The accumulated charge corresponding to the parasitic reactions Qloss can be written
as

∂Q loss
---------------
- = I loss
∂t

where Iloss (SI unit: A) is the loss current. The initial battery loss capacity is set to 0.
The remaining battery cell capacity Qcell (SI unit: C) is defined as

Q cell = Q cell,0 – Q loss

Using a lumped modeling approach, assuming limited knowledge about the internal
processes occurring inside the battery, any aging model will have to be empirical, not
being able to discriminate between different phenomena. Typically, capacity loss and
aging may be affected by the battery voltage, the capacity throughput, aging history
and temperature. To define a lumped aging rate we may write the sum of all parasitic
currents in the battery, resulting in a capacity loss, as

Q cell,0
I loss = ---------------- f E f I f aged f T
τ loss

where, τloss is a calendar aging time constant defining the rate of the parasitic reactions.
The factors fE, fI, faged, and fT are dimensionless aging factors, depending on the
battery voltage, battery current, aging history and temperature, respectively. Setting all
aging factors to 1 would result in a constant capacity loss from t = 0, reaching 0
remaining capacity when t = τloss, independent of battery SOC, capacity throughput,
aging history and temperature.

In many battery systems, it has been seen that high SOC values accelerate capacity loss.
Since a high SOC typically also results in a high battery voltage, one way of defining
fE for such systems is hence

170 | CHAPTER 3: BATTERY INTERFACES

 αF ( E OCV ( SOC, T ) + η act – E OCV ( T ) – E offset )
f E = exp  ---------------------------------------------------------------------------------------------------------------------------
RT

fE defined as above would correspond either to a parasitic electrochemical reduction

reaction occurring on the negative electrode, or an oxidation reaction occurring on the
positive electrode. The transfer coefficient α and offset potential Eoffset parameters
relate how the rate of the parasitic reactions changes when the battery voltage deviates
from the average open circuit voltage, E OCV ( T ) , defined as

E OCV ( T ) =  EOCV ( SOC, T )∂SOC

0

For many battery systems it is also often observed that the lifetime is closely related to
the amount of cycled equivalent full cycles (capacity throughput). A current
dependence term, resulting in a linear relation between the capacity fade and the
number of full cycles may be defined as

τ loss I cell
f I =  1 + H ------------------------
2Q cell,0

where H defines the additional (dimensionless) capacity loss induced by cycling. Note
that 2Qcell,0 corresponds to the capacity throughput of one full charge-discharge cycle.

The rate of the capacity fade may be slowed down as a result of products formed by
the parasitic reactions, for example by the formation of a mass transport limiting film
on the electrode particles. One way of defining a decelerating aging rate is to use the
following definition of faged:

1
f aged = ---------------------------------------------
Q loss
1 + ( G – 1 ) ----------------
Q cell,0

where G defines how many times the capacity fade rate has been reduced when all
capacity has been lost.

Finally, temperature is also known to be a crucial factor for aging. The temperature
factor fT is defined using an Arrhenius expression according to

Ea 1
f T = exp  – -------  ---- – ---------- 
1
 R  T T ref 

THEORY FOR THE LUMPED BATTERY INTERFACE | 171

 where Ea is the activation energy and Tref is a reference temperature.

Finally, it is reasonable to assume that the activation overpotential is not affected by the
parasitic reactions, and there is no need to explicitly include the parasitic reactions
when dealing with the main reaction potentials. This means that it is possible to treat
the activation overpotential independently of the parasitic reactions. The following
then holds good:

I cell = I ct + I dl + I loss ≈ I ct + I dl

SHORT CIRCUIT
In order to model a short circuit scenario inside a lumped battery, with known short
circuit resistance (inverse of conductance), one can use this node to define the short
circuit conductance Gshort. The short circuit current associated with this according to
the Ohm’s law is

I short = E cell G short

The corresponding Ishort is seen as a discharge current for the overall cell operation
and is deducted from the applied current:

I cell = I ct + I dl – I short

172 | CHAPTER 3: BATTERY INTERFACES

Theory for the Battery Pack
Interface
For the battery models of The Battery Pack Interface, refer to Theory for the Lumped
Battery Interface. Individual battery models are created for each disjoint set of
domains in the battery selection of the interface. All variables are given an additional
suffix i, where the index i ranges from 1 to N, where N is the number of disjoint sets
in the selection.

In the current conductors, the electric potential in the electrode phase φ s (SI unit: V)
is solved for using a charge balance based on Ohm's law.

The current density, is (SI unit: A/m2), is defined as

i s = – σ s ∇φ s

where σs is the electrical conductivity. The charge balance equation is expressed as

∇ ⋅ is = 0

The joule heating source term Qh (SI unit: W/m3) is defined as

Q h = – ( i s ⋅ ∇φ s )

The battery models, which are formulated as global 0D equations, are coupled to φ s
on the current collector on the negative and positive connectors (δΩneg,i and δΩpos,i,
respectively) separately for each battery i.

The coupling is achieved by defining two global electrical potential degrees of freedom
φ s,neg,i,, φ s,pos,i, and one degree of freedom for the individually applied battery
current Iapp,i (SI unit: A) and then solving the following set of equations. On the
negative and positive connectors, respectively,

φ s, neg,i = φ s

φ s, pos,i = φ s

Additionally,

E cell,i ( I app,i ) = φ s, neg,i – φ s, pos,i

THEORY FOR THE BATTERY PACK INTERFACE | 173

  ( n ⋅ i s ) dδΩ = – I app,i
δΩ neg,i

 ( n ⋅ i s ) dδΩ = I app,i
δΩ pos,i

For all subnodes to the Batteries node, except the Thermal Event subnode, refer to
Theory for the Lumped Battery Interface. The Thermal Event subnode is described
below.

All the boundary condition subnodes of the Current Conductors node are similar to
those described for the Current Distribution interfaces. See boundary nodes described
in Shared Nodes for Battery Interfaces.

THERMAL EVENT
The Thermal Event node can be used to define an event-based heat source. In
addition, the event may also induce changes in the ohmic overpotentials (internal
resistance) of the battery cells and/or induce cell short circuits.

Similarly to other nodes in the Battery Pack interface, individual events, heat sources
and associated state variables are created for each battery cell (disjoint set of domains)
in Thermal Event node selection.

To control the heat source released by the thermal event, an event time state variable
tte (SI unit: s) is used. The initial value of the event time variable is set to inf. The
thermal event is triggered by an Event condition, which could be when either the
maximum or average cell temperature exceeds a corresponding maximum or average
trigger temperature, or if the simulated time exceeds the explicit time that is
specified.When the event is triggered, the event time variable tte is set to the current
time t, in the case of maximum or average temperature event conditions. In the case
of explicit time event condition, the event time variable tte is set to the specified explicit
time texp. The event can only be triggered once per battery cell.

After the event has been triggered, the thermal event heat source Qh,te (SI unit: W) is
added to the total sum of all heat sources for the battery cell. The heat source should
be stated as a function of time elapsed after triggering of the event. Additionally, the
heat sources due to the added ohmic overpotential and short circuit are also included
appropriately.

174 | CHAPTER 3: BATTERY INTERFACES

DEFINING TEMPERATURE AND SOC-DEPENDENT BATTERY PARAMETERS
All battery parameters in the Battery Pack Interface, defined for instance in the Voltage
Losses, Cell Equilibrium Potentialand Thermal Event subnodes, need to be defined
using global (non-spatially resolved) values. Individual parameter dependencies, (that
is, per battery cell) on temperature and SOC are possible to define by the use of the
bp.T_cell and bp.SOC (without a suffix) variables. In the parameter expressions,
these variables are substituted internally to the corresponding global, but individually
defined bp.T_cell_X and bp.SOC_X variables, where the suffix X denotes the cell
number, ranging from 1 to the number of disjoint domains.

Note that bp.T_cell_X is defined as the as the average per cell of the temperature
expression under Model Input of the Voltage Losses node for each cell number X. If
Include concentration overpotential is active using Particle diffusion, bp.SOC is
substituted for the local SOC in the generalized particle in the Diffusion time-constant
parameter expression, and the average SOC in the particle for all other parameters.

THEORY FOR THE BATTERY PACK INTERFACE | 175

176 | CHAPTER 3: BATTERY 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

177
 The Primary and Secondary Current
Distribution Interfaces
In this section:

• The Primary Current Distribution • Electrode Line Current Source

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

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

The Primary Current Distribution and Secondary Current

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

Primary Current Distribution Interface

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

178 | 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, except that it also accounts for activation overpotentials. The
relation between charge transfer and overpotential can be described using arbitrary
kinetic expressions, such as Butler–Volmer and Tafel equations.

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

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

• Introduction to Electrochemistry Modeling

SETTINGS
The Label is the default physics interface name.

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

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

DOMAIN SELECTION

Domains that do not conduct current should be omitted from the

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

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 179

 OUT-OF-PLANE THICKNESS

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

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

CROSS-SECTIONAL AREA

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

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

CURRENT DISTRIBUTION TYPE

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

The selection between Primary or Secondary governs how electrode reactions are
modeled on interfaces between electrodes and electrolytes.

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

PHYSICS VS. MATERIALS REFERENCE ELECTRODE POTENTIAL

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

180 | 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
The interface uses Linear elements by default and this setting is recommended for most
problems. Certain types of problems, such as models using porous electrodes, or
current distribution problems in two dimensions or higher, may benefit in terms of
solution accuracy from using Quadratic elements.

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

all coupled interfaces.

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

• Electrochemical Reactions and the Difference Between a Primary and

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

Secondary Current Distribution: Orange Battery: Application Library

path Battery_Design_Module/Batteries,_General/orange_battery

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

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

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 181

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

• Domain Equations for Primary and Secondary Current Distributions

• Electrolyte Theory

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

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

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

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

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

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

182 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

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

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

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

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

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

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

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

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 183

 FILM RESISTANCE
See the Electrode Surface node.

• Domain Equations for Primary and Secondary Current Distributions

• Porous Electrode Theory

Capacity Fade of a Lithium-Ion Battery: Application Library path

Battery_Design_Module/Batteries,_Lithium-Ion/capacity_fade

Periodic Condition
Use the Periodic Condition to define a periodic relation between two boundaries — for
instance, in a model describing a repetitive unit cell.

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

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

For more information, see Periodic Boundary Conditions in the COMSOL

Multiphysics Reference Manual.

Thin Electrolyte Layer

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

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

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

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

184 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

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

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

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

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

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

CONSTRAINT SETTINGS
To display this section, click the Show 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.

THE PRIMARY AND SECONDARY CURRENT DISTRIBUTION INTERFACES | 185

 Electrode Line Current Source

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

For 2D components use it on points.

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

outside the symmetry axis.

ELECTRODE CURRENT SOURCE

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

Electrolyte Line Current Source

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

For 2D components use it on points.

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

outside the symmetry axis.

ELECTROLYTE CURRENT SOURCE

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

Electrode Symmetry Axis Current Source

For 2D axisymmetric components apply an Electrode Symmetry Axis

Current Source along the symmetry axis boundary.

ELECTRODE CURRENT SOURCE

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

186 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Electrolyte Symmetry Axis Current Source

For 2D axisymmetric components apply an Electrolyte Symmetry Axis

Current Source along the symmetry axis boundary.

ELECTROLYTE CURRENT SOURCE

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

Electrode Point Current Source

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

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

located on the symmetry axis.

ELECTRODE CURRENT SOURCE

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

Electrolyte Point Current Source

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

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

located on the symmetry axis.

ELECTROLYTE CURRENT SOURCE

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

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 | 187

 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

188 | 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 | 189

 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.

190 | 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 | 191

 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

Vanadium Redox Flow Battery: Application Library path

Battery_Design_Module/Flow_Batteries/v_flow_battery

192 | CHAPTER 4: ELECTROCHEMISTRY 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.

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) specified in the Diffusion section 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

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 193

 Porous Electrode
The Porous Electrode node sets up charge balances for the electrode and the pore
electrolyte in a porous electrode, and as well as the mass balance for the species in the
electrolyte.

Note that the node should be used for porous domains that conduct 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

194 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

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

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

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

The node is found from the Additional Sources submenu.

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

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

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

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

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

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 195

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

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

Ion Exchange Membrane

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

The node models the transport of all species added at the interface 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.

196 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

The node is applicable to external boundaries to electrolyte domains. 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 calculates the potential shift over the boundary based on the membrane charge
carrying species concentration, or User defined.

THE TERTIARY CURRENT DISTRIBUTION, NERNST-PLANCK INTERFACE | 197

 Shared Physics Features in the
Current Distribution Interfaces
Domain, Boundary, Pair, Edge, and Point Nodes for the
Electrochemistry Interfaces
This chapter describes various domain, boundary, edge, point, and pair nodes that are
common to several of the Electrochemistry Interfaces interfaces.

The nodes are available from the Physics ribbon toolbar (Windows users), Physics
context menu (Mac or Linux users), or right-click to access the context menu (all
users).The nodes and features described in this section are available for all the
Electrochemistry branch interfaces unless otherwise indicated.

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

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

198 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

• Charge-Discharge Cycling • Highly Conductive Porous
• Circuit Terminal Electrode

• Double Layer Capacitance • Initial Values for

Adsorbing-Desorbing Species
• Electric Ground
• Initial Values for
• Electric Potential
Dissolving-Depositing Species
• Electric Reference Potential
• Insulation
• Electrode
• Perforated Electrode Surface
• Electrode Current
• Internal Electrode Surface
• Electrode Current Density
• Line Mass Source1
• Electrode Current Source
• Non-Faradaic Reactions
• Electrode-Electrolyte Boundary
• Point Mass Source1
Interface
• Porous Electrode Reaction
• Electrode Power
• Porous Matrix Double Layer
• Electrode Potential
Capacitance
• Electrode Reaction
• Reference Electrode
• Electrode Surface
• Symmetry
• Electrolyte Current Density
• Thin Electrode Layer
• Electrolyte Current Source
• Electrolyte Potential
• External Short
• Harmonic Perturbation
1
For the Tertiary Current Distribution, Nernst–Planck interface, these nodes are
available and described for the Transport of Diluted Species interface.

In the COMSOL Multiphysics Reference Manual see Table 2-4 for links
to common sections and Table 2-5 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Theory for the Current Distribution Interfaces

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 199

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

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

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

Electrode Theory

Highly Conductive Porous Electrode

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

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

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

Electrode Current Source

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

∇ ⋅ is = Qs

where

i s = – σ s ∇φ s

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

200 | 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 | 201

 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

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

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

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

The Density and Molar mass, in conjunction with the reaction rates and stoichiometry,
defined in the Electrode Reaction subnodes, determine the normal electrode growth
rate.

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

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

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 203

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

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

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

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

Use The Surface Reactions Interface to model surface diffusion.

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

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

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

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

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

The frequency spectrum is specified in the study node.

204 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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.

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.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 205

 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
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.

206 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

For an example of this feature see Orange Battery: Application Library

path Battery_Design_Module/Batteries,_General/orange_battery.

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

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

Note that 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.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 207

 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.

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

208 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

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

(dimensionless), parameters will impact how much iloc will change upon changes in the
overpotential. In order to ensure thermodynamic consistency, αc cannot be user
defined when i0 is calculated From Nernst Equation (or by Mass action law in the Tertiary
Current Distribution interface). For this case, αc is defined automatically, based on the
number of participating electrons in the reaction, defined in the stoichiometry section.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 209

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

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

Cathodic Tafel Equation

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

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

Concentration Dependent Kinetics

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

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

The Concentration Dependent Kinetics expression type may be used in concentration

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

210 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

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

Thermodynamic Equilibrium (Primary Condition)

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

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

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

 νox Sox + ne  νred Sred

-
⇔ (4-1)
ox red

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

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

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 211

 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

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.

212 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

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

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

Perforated Electrode Surface

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

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

Internal Electrode Surface

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

Electrode domain
φs
Electrolyte domain
φl

Internal Electrode Surface

The node can be applied at interior boundaries between electrode and electrolyte
domains, and to external boundaries of porous electrode domains. Note that, due to
the high conductivity of many electrode materials, an Electrode domain can many

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 213

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

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

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

Electrolyte Current
The Electrolyte Current boundary condition sets the total current or average current
density of a boundary. The condition sets the total inward current without imposing
the current density distribution. It will set a constant electrolyte potential along the
given boundary, that satisfies the current value setting.

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

214 | 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.

• 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.

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

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 215

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

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

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

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

This node is available for the Secondary Current Distribution and Tertiary Current
Distribution, Nernst–Planck interfaces.It is also available and described here for the
Battery interface.

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.

216 | 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.

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

φ s = φ s, bnd

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

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

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

Electrode Current Density

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

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

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.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 217

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

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

• Electrode Current Theory

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

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

Electrode Power Theory

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.

218 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

Frequency Domain Perturbation Study Step in the COMSOL

Multiphysics Reference Manual

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

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

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

Electrode Potentials and Reference Electrodes

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

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

φ s = φ s, here

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

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

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 219

 Initial Values for Adsorbing-Desorbing Species
The node sets the initial values for the surface coverage of adsorbing-desorbing species
dependent variables.

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

Initial Values for Dissolving-Depositing Species

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

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

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

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

dissolving-depositing species present in the parent node.

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

220 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

Charge-Discharge Cycling
Use the Charge-Discharge Cycling node to specify a load cycling boundary condition in
time-dependent simulations, where the switch between charge and discharge depends
on the resulting cell voltage (or current). The node may for instance be used for
constant-current/constant-voltage (CCCV) cycling in battery simulations.

The node is applicable to external boundaries to electrode domains, and should

typically be applied on the positive electrode of the cell.

Depending on the Start Mode setting, the node will either start in Charge or Discharge
mode.

Each cycle always start with a constant Discharging/Charging current period, which ends
when the corresponding Minimum/Maximum voltage is reached (the voltage is defined
with respect to ground).

After the constant Discharging/Charging current period, you may also Include
constant voltage discharging/charging periods, which will end when the specified Lower
cutoff current or Upper cutoff current is reached. At the end of each cycle, you can also
Include rest periods, specifying the Resting time.

The node also defines a cycle counter variable (xxx.cdc1.cycle_counter, where xxx
is the physics interface tag), which may be used in postprocessing or when defining
Stop Condition in the time-dependent solver to end the simulation when a specified
number of cycles has been reached.

SHARED PHYSICS FEATURES IN THE CURRENT DISTRIBUTION INTERFACES | 221

 Note: For more complex load cycles you may use The Events Interface to set up the
cycling behavior.

For an example how to use this node, see Capacity Fade of a

Lithium-Ion Battery

The Events Interface

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.

• Connecting to Electrical Circuits

222 | 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 | 223

 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.

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

THE ELECTRODE, SHELL INTERFACE | 225

 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.

226 | 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 φ s = 0 .

THE ELECTRODE, SHELL INTERFACE | 227

 EDGE OR POINT SELECTION

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

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

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

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

EDGE OR POINT SELECTION

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

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

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

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

228 | 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 | 229

 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

230 | 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 ∇φ l + c i u = J i + c i u

where

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

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

J i = – D i ∇c i – z i u m, i Fc i ∇φ l (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 ∇φl .
2 2
il = –F

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

define a constant electrolyte conductivity as:

 zi um, i ci
2 2
σl = F

the current density in the electrolyte can be written as

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 231

 i l = – σ l ∇φ l

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

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

∇ ⋅ il= 0

In a pore electrolyte, the homogenization used in the theory for porous

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

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

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

∇ ⋅ ik = Qk

with

i k = – σ k ∇φ k

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

Electrochemical Reactions and the Difference Between a Primary and

a Secondary Current Distribution
Both the primary and secondary current distribution models assume an electrolyte that
conducts current according to Ohm's law, with a constant conductivity. The difference
between a primary and a secondary current distribution lies in the description of the

232 | 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 ηm, is the following:

η m = φ s – φ l – E eq, m

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

In the Primary Current Distribution interface, the electrochemical reactions are

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

φ l = φ s – E eq, m

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

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

In the Secondary Current Distribution interface, the electrochemical reactions are

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

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

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 233

 where iloc,m denotes the local charge transfer current density for reaction m, i0,m the
exchange current density, αa,m the anodic transfer coefficient, αc,m 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.

234 | 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 each 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 material balances give one equation per unknown species concentration.

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.)

There is one more unknown dependent in the variable, the electrolyte potential, which
requires an additional equation to close the system. This equation is the
electroneutrality condition, which follows from dimensional analysis of Gauss’s law. In
a typical electrolyte solution, it is accurate over lengths greater than a few nanometers:

 zi ci = 0

Using the electroneutrality condition reduces the number of dependent concentration

variables by one.

Further, by combining the electroneutrality condition with the sum of all species flux
vectors and the species mass balance equation, multiplied by the individual species
charges, results in expressions for the current vector and a current balance equation,
respectively.

The expression for the current density in the electrolyte, il, reads:

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 235

 n n

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

whereas current balance in the electrolyte, used for solving for the electrolyte potential,
then becomes:

∇ ⋅ il = Ql

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

The charge transfer reaction can be parameterized by arbitrary functions of the

concentrations of the species in the redox couple and the local electric and electrolyte
potentials. The most common way to describe the reaction kinetics is to use a
Butler-Volmer expression for the charge transfer current density. See The
Butler-Volmer Equation.

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

Mass Fluxes and Sources Due to Electrochemical Reactions

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

 νox Sox + ne  νred Sred

-
⇔
ox red

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

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

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

236 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

where iloc, m is the local current density (SI unit: A/m2) of the electrochemical
reaction, nm the number of participating electrons and F (SI unit: C/mol) is the
Faraday constant. Note that iloc, m denotes the current density perpendicular to the
electrode surface.

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

Ni = Ni ⋅ n

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

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

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

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

Deposition-Dissolution Rates, Growth Velocities, and Thicknesses on

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

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

Mi ν i, m i loc, m
v dep, tot =  ------
ρi  nm F
- -------------------------- (4-3)
i m

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

This velocity may be used in deforming geometry models as a boundary condition for
the geometry deformation by assuming that dissolution or deposition always occurs in

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 237

 the normal direction to an electrode boundary, with the velocity being directed into
the electrolyte domain:

∂x
⋅ n = v dep, tot
∂t

In a time-dependent simulation one may also introduce a surface concentration

variable, cs,i (mol/m2) on the boundary and calculate the accumulated surface
concentration change by using a local ordinary differential equation (ODE):

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

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

Mi
s tot =  ------
-c .
ρ i s, i
i

Stoichiometric Coefficients for Double Layer Capacitive Charging

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

Consider an overall reaction as:

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

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

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

238 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

Δφ s, film = i tot R film

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

η m = φ s – Δφ s, film – φ l – E 0, m

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

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

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

Equilibrium Potentials and the Nernst Equation

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

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

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

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

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

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 239

 ΔG
E eq = – --------
nF

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

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

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

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

Electrode Kinetics Expressions

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

THE EQUILIBRIUM POTENTIAL AND THE OVERPOTENTIAL

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

η = φ s – φ l – E eq

where Eeq denotes the equilibrium potential.

THE BUTLER-VOLMER EQUATION

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

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

240 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

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

Concentration Dependence and the Exchange Current Density

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

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

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

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

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

η ref = φ s – φ l – E eq, ref .

This latter form of the Butler-Volmer equation, where the reference overpotential and
the exchange current density do not vary with concentration, is usually preferable
numerically.

The law of mass action is usually not suitable for defining 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):

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 241

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

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

αa νi
ξ a, i = γ i + -----------
n

and

αc νi
ξ c, i = γ i – ----------- .
n

Exchange Current Density and Rate Constants

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

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

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

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

Generic Concentration Dependent Butler-Volmer Type Kinetics

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

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

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

reduced and oxidized species in the reaction. Note that if CO ≠ CR when η = 0, this
kinetics expression results in iloc ≠ 0, thus violating the concept of equilibrium. This

242 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

may result in thermodynamical inconsistencies, for instance when coupling an
electrochemical model to heat transfer.

SIMPLIFICATIONS OF THE BUTLER-VOLMER EQUATION

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

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

Anodic and Cathodic Tafel Equations

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

The anodic Tafel equation is implemented as follows:

η ⁄ Aa
i loc = i 0 ⋅ 10

where Aa (SI unit: V) is the so-called Tafel slope. Aa relates to the corresponding
transfer coefficient as follows

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

The cathodic Tafel expression is defined according to:

η ⁄ Ac
i loc = – i 0 ⋅ 10

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

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

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 243

 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
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 CONCENTRATIONS

Consider a concentration-based kinetic expression

dc ν
= r = – kc
dt

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

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

A second case to consider is when ν is an even integer larger than 1. The rate then will
become increasingly negative for negative values of c, resulting in an “exploding”
solution, iterating c toward minus infinity. The standard solution for these cases, which
also works for noninteger ν values larger than 1, is to change the expression c in the

244 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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 values.

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

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

ν
r = – kc c > c lim

υ–1
r = – kcc lim c < = c lim

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

Theory for Specific Current Distribution Feature Nodes

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

∇ ⋅ il = 0

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

The definition of the current density vector depends on the equation formulation of
the electrolyte charge transport, as discussed above in Domain Equations for Primary

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 245

 and Secondary Current Distributions and Domain Equations for Tertiary Current
Distributions Using the Nernst–Planck Equations and Electroneutrality.

• For the Primary and Secondary Current Distribution interfaces, see

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

POROUS ELECTRODE THEORY

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

∇ ⋅ i l = Q l and ∇ ⋅ i s = Q s

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

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

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

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

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

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

246 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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
means that the local current density expression above is also included in the material
balances as a reaction term, Ri, by using Faraday’s laws for each of the species that take
part in charge transfer reactions.

• For the Primary and Secondary Current Distribution interfaces, see

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

ELECTRODE REACTIONS THEORY

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

il ⋅ n =  iloc, m
m

is ⋅ n = –  iloc, m
m
2
where iloc,m (A/m ) is the Electrode Reaction current density of the charge transfer
electrode reaction of index m, il the current density vector in the electrolyte and is the
current density vector in the electrode.

POROUS ELECTRODE REACTIONS THEORY

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

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 247

 ∇ ⋅ il =  Av iloc, m
m

∇ ⋅ is = –  Av iloc, m
m

where Av is the specific surface area of the electrocatalyst.

Porous Electrode Reaction

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

∇ ⋅ is = 0

where is denotes the current density vector according to:

i s = – σ s ∇φ s

and where σs denotes the electrical conductivity and φ s the potential of the electron
conducting (metal) phase.

ELECTROLYTE CURRENT DENSITY THEORY

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

i l ⋅ n = i n, l

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

i l = i l, bnd

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

Electrolyte Current Density

248 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

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

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

 il ⋅ n ds = I n, l
∂Ω

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

ELECTRODE CURRENT THEORY

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

 is ⋅ n ds = I n, s
∂Ω

where

i s = – σ s ∇φ s

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

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

ik ⋅ n = 0

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 249

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

The Symmetry boundary condition for the Tertiary Current Distribution, Nernst–
Planck interface imposes a no-flux condition for the molar flux of species at a
boundary. The condition is expressed as follows:

Ji ⋅ n = 0

ELECTRODE CURRENT DENSITY THEORY

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

i s ⋅ n = i n, s

where

i s = – σ s ∇φ s

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

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

i s = i s, bnd

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

ELECTRODE POWER THEORY

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

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

φ s = φ s, bnd on ∂Ω

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

∂Ω

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

250 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

For an average power condition, Ptotal is calculated by:

P total = P avg A

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

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

Electrode Power

ION EXCHANGE MEMBRANE THEORY

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

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

For Nernst Planck with electroneutrality, the electroneutrality condition reads

ρ fix + F  zi ci = 0

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

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

μ i = RT ln a i + φ l z i F

THEORY FOR THE CURRENT DISTRIBUTION INTERFACES | 251

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

At equilibrium the electrochemical potentials on each side of the free electrolyte -

ion-exchange membrane interface are equal.

Setting the species activity to equal the concentration and denoting the liquid
electrolyte phase and a ion-exchange membrane phases as 1 and 2, respectively, the
Donnan potential, Δφ (V), describes the relation between the concentration of a
species, ci (mol/m3), at each side of the boundary and the electrolyte potentials:

c i, 1
Δφ l = φ l, 1 – φ l, 2 = – -------- ln  ---------
RT
z i F  c i, 2

which may be rearranged to

z i F ( φ l, 1 – φ l, 2 )
c i, 2 = c i, 2 exp  – ---------------------------------------
RT

The molar flux of each species in the liquid electrolyte is continuous over the
membrane-liquid interface

n ⋅ J i, 1 = n ⋅ J i, 2

Since the total current density is the sum of all species fluxes, times the individual
species charges, the current densities Il in the normal direction n of the
membrane-liquid interface boundary is also continuous:

n ⋅ I l, 1 = n ⋅ I l, 2

Reference
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.

252 | 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 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 | 253

 Joule Heating Due to Charge Transport
As the charged particles are transported in an electric field, electrical energy is
converted into heat. The heat source terms for Joule heating in the electrode and
electrolyte phases are computed similarly by multiplying the current vector to the
gradient of the potential field variable according to

Q JH = – ( i s ⋅ ∇φ s + i l ⋅ ∇φ 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 Energy - Electrical Energy Generated

Using Faraday’s law for an electrode reaction, m, at the interface between the electron
and ion conducting phase this corresponds to

ΔH m ΔG m
Q m =  ------------- –  ------------- – η m, tot  i m (4-5)
 nm F  nm F 

where ΔHm is the enthalpy change of the reaction, and ΔGm is the Gibbs free energy
of the reaction, ΔGm, defined as

ΔG m = ΔH m – TΔS m

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

TΔS m
Q m =  η 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, ηm,tot,(including potential

effects from film resistances and similar), defined as

η m, tot = φ s – φ l – E eq, m

The equilibrium potential is related to ΔGm in the following way:

254 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

 ΔG m
E eq, m = – -------------
nm F

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

∂E eq, m ΔS m
------------------
- = -----------
-
∂T nm F

the local heat source due to the electrochemical conversion process becomes

∂E eq, m
Q m =  η m, tot + T ------------------- i m
 ∂T 

Alternatively, by defining the thermoneutral voltage of the reaction as

ΔH m
E therm, m = – -------------
nm F

one may also define the heat source as

Q m = ( η m, tot + ( E eq, m – E therm, m ) )i m

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

Q EC =  Qm
m

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

Q TOT, p =  av, m Qm + QJH

m

Heating Due to Heat of Mixing

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

THEORY FOR ELECTROCHEMICAL HEAT SOURCES | 255

 in the Electrochemistry interfaces, except for intercalating porous electrodes in the
battery interfaces (see next section).

Heat of Mixing in Intercalating Electrodes

For intercalating porous electrodes in the battery interfaces, the heat of mixing qmix,i
(W/m3) of a species of index i is defined as (see Ref. 3)

q mix, i = – J i ⋅ ∇H i

where Ji (mol/(m2s)) is the molar flux and Hi (J/mol) is the molar enthalpy.

This expression could be seen as a species transport version of Joule heating in an

electronic conductor, for which the heat source is defined as the current density
multiplied by the gradient of the potential.

Generally, for an intercalation material, two species are considered: the intercalated
species, denoted with index s, and the holes, denoted with index θ.

The flux of the two species are equal and opposite.

Js = –JΘ

We now define the total heat of mixing as the sum of the contributions from the two
species and write

q mix = q mix, s + q mix, Θ = – J s ⋅ ∇ ( H s – H Θ )

The absolute value of the individual molar enthalpies are generally not known.
However, the difference of the gradients of the molar enthalpies are related to the
thermoneutral voltage, Etherm (V) of the intercalation reaction.

The thermoneutral voltage is defined as

ΔH ( ΔG + TΔS ) dE eq
E therm = – --------- = – -------------------------------- = E eq – T -------------
F F dT

where ΔH is the change of molar enthalpy of the redox reaction.

In the case of lithium intercalation the redox reaction is

+ -
Li + e ⇔ Li(s)

with index s = Li(s) so that

256 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

 ΔH = H Li(s) – H Li+ – H θ

We now note that, if assuming the equilibrium potential to be independent of the

electrolyte lithium ion concentration,

dE eq, therm
∇ ( H s – H θ ) = – ∇ ( FE eq, therm ) = – F --------------------------- ∇c s
dc s

and finally we get

dE eq, therm
q mix = – J s ⋅  – F --------------------------- ∇c s
 dc s 

which is added to the expression for QTOT,p above.

Total Overpotential Calculation for Concentration Dependent

Kinetics
When using the Concentration Dependent kinetics option, in the Porous Electrode
Reaction and Electrode Reaction nodes, the equilibrium potential is typically a
constant referring to a reference state, and the concentration dependence of the
kinetics is accounted for only in the pre-exponential terms according to

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

where

η m = φ s – φ l – E eq, m

A result of this is that, when the pre-exponential factors CO,m and CR,m differ due to
concentration gradients, we at zero activation overpotential may have a net
charge-transfer current density flowing over the electrode-electrolyte interface. This
local current density obviously should give rise to a heat source. The solution is to add
a concentration overpotential term to the total overpotential when calculating the heat
sources.

When using the Concentration Dependent kinetics option, the overpotential, used in
the irreversible heat term above, is calculated as follows:

η m, tot = φ s – φ l – E eq, m + η m, conc

THEORY FOR ELECTROCHEMICAL HEAT SOURCES | 257

 where

RT C O, m
η m, conc = ------------ ln --------------
n m F C R, m

If the number of electrons is not available,

nm = α · + α c, m
a, m

is assumed.

References
1. Bernardi et al “A General Energy Balance for Battery Systems”, Journal of the
Electrochemical Society, 132 (1985), 5-12

2. Thomas et al “Thermal Modeling of Porous Insertion Electrodes”, Journal of the

Electrochemical Society, 150 (2003), A176-A192

3. Electrochemical Systems, Newman and Thomas-Alyea, Chapter 13 Thermal Effects

258 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

Theory for the Electrode, Shell
Interface
The Electrode, Shell Interfacedefines electrode current conduction in a thin shell on a
boundary. The electrolyte current distribution in the adjacent domain is typically
solved for by a separate physics interface.

In this section:

• Governing Equations
• Coupling to Other Physics Interfaces

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

∇ T ⋅ ( si s ) = – i n (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 σ s φ s (4-8)

where σs is the electric conductivity (SI unit: S/m). The next section discusses
Coupling to Other Physics Interfaces.

Coupling to Other Physics Interfaces

ELECTRODE POTENTIAL IN OTHER PHYSICS INTERFACES

Typically the boundary electric potential in the Electrode Surface node is set to the
electric potential in the Electrode, Shell interface.

ELECTRODE REACTION CURRENTS

The sum of currents can be coupled to other electrochemistry interfaces, calculating
in as

THEORY FOR THE ELECTRODE, SHELL INTERFACE | 259

 i n = i tot

where itot (SI unit: A/m2) is the sum of all electrode currents in the coupled
Electrochemistry interface.

ELECTRODE LAYER THICKNESS

The electrode thickness, s, can typically be coupled to an External Depositing
Electrode (External Corroding Electrode) node in the Electrodeposition, Moving
Mesh (Corrosion, Moving Mesh) interface, in that case s is calculated as

s = s 0 + Δs tot (4-9)

where s0 is the initial electrode layer thickness, and Δstot is the electrode thickness
change, calculated by the coupled Electrochemistry interface.

HEAT SOURCE
The electron conduction gives rise to a Joule heating source QH (SI unit: W/m2)
according to

Q H = – si s ⋅ ∇ t φ s

260 | 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 | 261

 electrolyte. The purpose of the supporting electrolyte is to increase the conductivity of
the solution, and hence to eliminate the electric field from the electrolyte.

A negligible electric field provides two advantages for electroanalysis:

• The voltage due to the resistance of the electrolyte when the cell draws current
(“ohmic drop”) is minimal. Therefore, the potential difference applied across the
electrochemical cell is localized at the electrode–electrolyte interfaces, and so the
activation overpotential perceived by the redox couple at this interface is almost
exactly proportional to the applied cell voltage. The kinetic behavior of the
electrochemical cell then has no explicit dependence on the magnitude of the drawn
current.
• The contribution of migration to the transport of charged chemical species is
negligible compared to the contribution of diffusion (and of convection, in a forced
flow). Therefore the transport properties of the system are linearized, and they do
not depend on the magnitude of the drawn current.

These properties greatly simplify the design and analysis of electroanalytical

experiments. Therefore, the use of a supporting electrolyte is very common in
electrochemical sensing and electroanalysis.

The amount of supporting electrolyte required for the assumption of zero

electric field to be sound is dependent on the system. Typically it becomes
valid when the concentration of inert salt exceeds the concentration of
analyte by a factor of 10–100, but this is not always the case.

Even for the conductivities of electrolyte solutions in the presence of excess supporting
electrolyte, the electric field is not negligible if significant current density is drawn.
Electroanalysis typically draws small currents because the purpose is measurement. In
processes where an electrochemical reaction is driven — such as electrolysis,
electrodeposition, batteries, and fuel cells — current densities are typically much larger,
so that the desired extent of reaction is achieved in a reasonable time. Under these
conditions, significant electric fields are likely and other charge conservation models
should be used instead of the Electroanalysis option.

Domain Equations for the Electroanalysis Case

The Electroanalysis option assumes that the electric field is zero, and so the electrolyte
potential is constant. Since you can arbitrarily choose to ground the electrolyte
potential at any point, set it to φ l = 0 .

262 | 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 ∇φ l + c i u = J i + c i u

Here Ji denotes the molar flux relative to the convective transport.

At zero electric field, this reduces to:

N i = – D i ∇c i + c i u (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 | 263

 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:

η m = φ s – φ l – E eq, m

This is the potential difference perceived by a redox couple, measured against the
equilibrium potential of the couple; it provides the thermodynamic driving force for
an electrochemical reaction by faradaic charge transfer between the electrode and the
electrolyte domains.

Subject to the approximation of constant electrolyte potential ( φ l = 0 ), this equation

reduces to:

η m = φ s – E eq, m

The activation overpotential is independent of the properties of the adjacent

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

264 | 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:

ν i, m i m
Ni =  -----------------
nm F
- (4-13)
m

where νi,m is the stoichiometric coefficient of species i with respect to reaction m (in
the reductive direction), and nm is the number of transferred electrons. F is the
Faraday constant, which is the charge on a mole of electrons (96485.3365 C/mol).

The surface flux is applied as a boundary condition:

Ni = Ni ⋅ n (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 Double Layer Capacitance:

i total =  iloc, m + inf

m

The experimentally measurable total current I (SI unit: A) drawn at an electrode can
be computed by integration of the local current density (SI unit: A/m2) across the
electrode area:

THEORY FOR ELECTROANALYSIS | 265

 I total =  itotal ds
∂Ω

Domain Equations for the Electroanalysis Case

The Electroanalytical Butler-Volmer Equation

A one-electron electrochemical reaction between two solution-phase species can be
–
written as a reduction Ox + e ↔ Red .

Ox and Red represent the oxidized and reduced forms of the chemical species,
respectively.

The most general equation to describe the rate of this reaction as it proceeds at an
electrode surface is the electroanalytical Butler-Volmer equation:

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

where k0 is the heterogeneous rate constant (SI unit: m/s) and αc is the (cathodic)
transfer coefficient (dimensionless). For a one-electron reduction, the anodic and
cathodic transfer coefficients are related as follows α a + α c = 1 .

When the current is zero, the electroanalytical Butler-Volmer equation can be

rearranged to the thermodynamic Nernst equation relating the equilibrium
concentrations of the reacting species:

– FE eq
c Red = c Ox exp  ----------------
 RT 

Where the flux of the reacting species is negligible compared to the concentration of
these species, the concentrations are roughly constant (cRed ~ cOx ~ c). This converts
Equation 4-15 into the Butler-Volmer equation written in terms of an exchange
current density i0 (SI unit: A/m2):

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

The exchange current density i0 (SI unit: A/m2) is then related to the heterogeneous
rate constant as i 0 = k 0 Fc .

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

φ s, CE :  i tot dS = 0 (4-16)
electrodes

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

expression(s) on the counter electrode.

η m = φ s, CE – E eq, m (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 | 267

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

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

η = φ s – φ l – E eq (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, φ s – φ l , that

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

In this section:

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

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

268 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

 φ s, ref = φ l + E eq, ref (4-19)

where φ s , ref (SI unit: V) is the electric potential of the reference electrode and Eeq, ref
(SI unit: V) is the equilibrium potential of the reference electrode reaction.

The electric potentials of the electrodes in the electrochemical cell can then be defined
with respect to the reference electrode according to:

E vs ref = φ s – φ s, ref (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

φ s, bnd = E vs ref + φ s, ref (4-21)

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

Nodes for Handling Electrode Potentials and Reference Electrodes

The Reference Electrode node is a point feature applicable to electrolyte domains (in
all the Electrochemistry interfaces). It defines a global electric reference potential
φ s , ref (SI unit: V) according to Equation 4-19. The φ s , ref can be used in the
Electrode Potential feature for setting the electric potential of an electrode boundary
with respect to the reference potential. The variable Evs ref (SI unit: V), according to
Equation 4-20, is also defined in all electrode domains.

ELECTRODE POTENTIALS AND REFERENCE ELECTRODES | 269

 The Electric Reference Potential node is a point feature applicable to electrode
domains (in all the Electrochemistry interfaces). It defines a global electric reference
potential φ s , ref (SI unit: V) equal to the dependent variable φ s (SI unit: V) in the
point. The φ s , ref can be used in the Electrode Potential feature for setting the electric
potential of an electrode boundary with respect to the reference potential.

Whenever a φ s , ref is defined, the variable Evs ref (SI unit: V), according to
Equation 4-20, is also defined in all electrode domains.

The Electrode Potential is a boundary condition feature, applicable to external

boundaries of electrode domains (in all the Electrochemistry interfaces). It sets a
boundary condition for the electric potential with respect to a defined reference
potential according to Equation 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.

270 | CHAPTER 4: ELECTROCHEMISTRY INTERFACES

 5

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
• The Electrical Circuit Interface
• Theory for the Electrostatics Interface
• Theory for the Electric Currents Interface
• Theory for the Electrical Circuit Interface

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

271
 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 when it is used 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.

272 | CHAPTER 5: 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 | 273

 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 ) = ρs

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

n ⋅ [ ( ε 0 ∇V – P ) 1 – ( ε 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 5-1 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.

274 | CHAPTER 5: 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 • Symmetry Plane (for Electric Field)
• Thin Low Permittivity Gap
• Zero Charge (the default boundary
condition)
1
This feature is available with the Piezoelectricity multiphysics interface.
2
Requires either the Acoustics Module, MEMS Module, or Structural Mechanics
Module.

THE ELECTROSTATICS INTERFACE | 275

 Table 5-1 lists the interior and exterior boundary conditions available with this physics
interface. It also includes edge, point, and pair availability.
TABLE 5-1: 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
Symmetry Plane x not applicable
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.

276 | CHAPTER 5: 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 = ε0εrE. Then
the default is to take the Relative permittivity εr (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 = ε0E + 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 = ε0εrE + Dr, where Dr
is the remanent displacement (the displacement when no electric field is present).
Then the default is to take the Relative permittivity εr (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 either the Acoustics Module, or MEMS Module, or

Structural Mechanics Module. See the individual documentation for
information.

THE ELECTROSTATICS INTERFACE | 277

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

CONDUCTION CURRENT
By default, the Electrical conductivity σ 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 σ in the field or matrix.
• For Linearized resistivity the default Reference temperature Tref, and Resistivity
temperature coefficient α, and Reference resistivity ρ0 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.

278 | CHAPTER 5: AC/DC INTERFACES

Space Charge Density
The Space Charge Density node adds a space charge density ρ, 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 ρv (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 | 279

 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 = ρs , n ⋅ ( D1 – D2 ) = ρs

Specify the surface charge density ρs 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 ρs (SI unit: C/m2).

280 | CHAPTER 5: AC/DC INTERFACES

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

–n ⋅ D = ρs

where ρs is the solution of the following distributed ODE on the boundary:

dρ 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)
sand the Normal electron current density n·Je (SI unit: A/m2).

Symmetry Plane (for Electric Field)

The Symmetry Plane node adds a boundary condition that represents symmetry or
antisymmetry in the electric field, depending on which option is chosen.

SYMMETRY TYPE
Choose between Symmetry and Antisymmetry for the electric field. If Symmetry is
chosen, the boundary condition is

n⋅E = 0

THE ELECTROSTATICS INTERFACE | 281

 which states that the normal component of the electric field is zero. If Antisymmetry is
chosen, the boundary condition becomes

n×E = 0

which states that the tangential component of the electric field is zero.

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).

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 section, which you activate by right-clicking
the Periodic Condition node and select Manual Destination Selection. With that section,
the boundaries which constitute the source and destination surfaces can be manually
specified.

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.

282 | CHAPTER 5: AC/DC INTERFACES

BOUNDARY SELECTION

The software usually automatically identifies the boundaries as either source boundaries or
destination boundaries, as indicated in the selection list. This works fine for cases like opposing
parallel boundaries. In other cases, right-click Periodic Condition and select Manual Destination
Selection to control the destination. By default it contains the selection that COMSOL
Multiphysics identifies.

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.

DESTINATION SELECTION
This section is available for specifying the destination boundaries, if needed, when the
Manual Destination Selection option is selected in the context menu for the Periodic
Condition node. You can only select destination boundaries from the union of all source
and destination boundaries.

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

• Continuity to make the 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.

ORIENTATION OF SOURCE
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.

ORIENTATION OF DESTINATION
This section appears if the setting for Transform to intermediate map in the Orientation
of Source section is changed from the default value, Automatic, and Advanced Physics

THE ELECTROSTATICS INTERFACE | 283

 Options is selected in the Show More Options dialog box. For information about the
Orientation of Destination section, see Orientation of Source and Destination.

Thin Low Permittivity Gap

Use the Thin Low Permittivity Gap node

ε0 εr
n ⋅ D 1 = ---------- ( V 1 – V 2 )
d
ε0 εr
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 εr. 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 εr (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.

284 | CHAPTER 5: AC/DC INTERFACES

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)

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.

THE ELECTROSTATICS INTERFACE | 285

 POINT SELECTION

Beware that constraining the potential on points usually yields a current

outflow that is mesh dependent.

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)

286 | CHAPTER 5: AC/DC INTERFACES

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.

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 one unit
area is typically not representative for the actual domain. Instead, it describes a unit
area that makes the 1D equation identical to the equation used for 3D components.

THE ELECTROSTATICS INTERFACE | 287

 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.

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

either the Acoustics Module, or MEMS Module, or 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

288 | CHAPTER 5: AC/DC INTERFACES

behaves like a dielectric and not a piezoelectric. In this case, the default is to take the
Relative permittivity εrS (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 | 289

 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. The interface is typically used to
model good conductors for which Ohm’s law applies. It is not suitable for modeling
poor conductors like air and insulators.

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.

290 | CHAPTER 5: AC/DC INTERFACES

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.

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 m2 is typically not representative for a small domain. Instead it describes a unit area
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.

THE ELECTRIC CURRENTS INTERFACE | 291

 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

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 5-1 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.

292 | CHAPTER 5: AC/DC INTERFACES

AVAILABLE NODES
These nodes are available for this physics interface, listed in alphabetical order. Also see
Table 5-1 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
• Symmetry Plane (for Electric Field)

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 | 293

 Table 5-1 lists the interior and exterior boundary conditions available with this physics
interface. It also includes edge, point, and pair availability.
TABLE 5-2: 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
Symmetry Plane 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 σ (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

294 | CHAPTER 5: AC/DC INTERFACES

electrical conductivity σ in the field or matrix. The default is 0 S/m. If type of
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
σ = ---------------------------------------------------
ρ 0 ( 1 + α ( T – T ref ) )

where ρ0 is the resistivity at the reference temperature Tref, and α is the temperature
coefficient of resistance, which describes how the resistivity varies with temperature.

The default Reference resistivity ρ0 (SI unit: Ω⋅m), Reference temperature Tref
(SI unit: K), and Resistivity temperature coefficient α (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 Ω⋅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, see Constitutive Relation D-E as
described for the node for the Electrostatics interface. The constitutive relations
specific to Electric Currents are:

THE ELECTRIC CURRENTS INTERFACE | 295

 • Loss tangent, loss angle: uses the constitutive relation D = ε0ε'(1 − jtanδ)E. Specify
the Relative permittivity (real part) ε' (dimensionless) and Loss angle δ (SI unit: rad).
• Loss tangent, dissipation factor: uses the constitutive relation D = ε0ε'(1 − jtanδ)E.
Specify the Relative permittivity (real part) ε' (dimensionless) and the Dissipation
factor tanδ (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 = σE + 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.

296 | CHAPTER 5: 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 | 297

 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.

298 | CHAPTER 5: 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 σs, the
relative permittivity εr and layer thickness ds, or directly with the surface resistance ρs
and capacitance Cs. Assuming DC currents, the equation is:

σs
n ⋅ ( J 1 – J 2 ) = ----- ( V – V ref )
ds
1
n ⋅ ( J 1 – J 2 ) = ----- ( V – V ref )
ρs

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 σ (SI unit: S/m) and Relative permittivity εr
(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 ρs
(SI unit: Ω·m2) and the Surface capacitance Cs (SI unit: F/m2). The default surface
impedance is 1·10−8 Ω·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 | 299

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

σ
n ⋅ J 1 = ------ ( V 1 – V 2 )
ds
σ
n ⋅ J 2 = ------ ( V 2 – V 1 )
ds
1
n ⋅ J 1 = ----- ( V 1 – V 2 )
ρs
1
n ⋅ J 2 = ----- ( V 2 – V 1 )
ρs

The first two equations refer to a layer impedance specified using the bulk material
conductivity σs and the layer thickness ds, while the last two equations refer to the case
in which the surface resistance ρs 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 σ (SI unit: S/m) and Relative permittivity εr
(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 ρs (SI
unit: Ω·m2) and the Surface capacitance Cs (SI unit: F/m2). The default surface
impedance is 1·10−8 Ω·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

300 | CHAPTER 5: 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 | 301

 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.

302 | CHAPTER 5: 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 | 303

 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 Πl (SI unit: m4/
(s⋅A2); note that this is equivalent to Ω⋅m/Pa).
• For a Elastoresistance form, select an Elastoresistance coupling matrix Ml
(SI unit: Ω⋅m).

304 | CHAPTER 5: AC/DC INTERFACES

T he E le c tr i c a l Ci rcu i t In t erface
The Electrical Circuit (cir) interface ( ), found under the AC/DC branch ( ) when
adding a physics interface, is used to model currents and voltages in circuits including
voltage and current sources, resistors, capacitors, inductors, and semiconductor
devices. Models created with the Electrical Circuit interface can include connections
to distributed field models. The physics interface supports stationary,
frequency-domain and time-domain modeling and solves Kirchhoff’s conservation
laws for the voltages, currents and charges associated with the circuit elements.

When this physics interface is added, it adds a default Ground Node feature and
associates that with node zero in the electrical circuit.

Circuit nodes are nodes in the electrical circuit (electrical nodes) and
should not be confused with nodes in the Model Builder tree of the
COMSOL Multiphysics software. Circuit node names are not restricted
to numerical values but can contain alphanumeric characters.

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 cir.

RESISTANCE IN PARALLEL TO PN JUNCTIONS

For numerical stability, a large resistance is added automatically in parallel to the pn
junctions in diodes and BJT devices. Enter a default value for the Resistance in parallel
to pn junctions Rj (SI unit: Ω). The default value is 1·1012 Ω.

CREATE UNIQUE NODES FOR NEW DEVICES

When this setting is selected (the default), newly added devices will be assigned unused
node names. The devices will be disconnected from the rest of the circuit and the
nodes should be updated to reflect the actual circuit connections. When this setting is

THE ELECTRICAL CIRCUIT INTERFACE | 305

 deselected, new devices will be connected to the lowest-numbered nodes starting from
0.

ELECTRICAL CIRCUIT TOOLBAR

The following nodes are available from the Electrical Circuit ribbon toolbar (Windows
users), Electrical Circuit context menu (Mac or Linux users), or right-click to access the
context menu (all users):

For step-by-step instructions and general documentation

descriptions, this is the Electrical Circuit toolbar.

• Ground Node • Subcircuit Definition

• Voltmeter • Subcircuit Instance
• Ampère Meter • Mutual Inductance
• Resistor • Transformer
• Capacitor • Battery Open Circuit Voltage
• Inductor • Resistor-Capacitor Couple
• Voltage Source • NPN BJT and PNP BJT2
• Current Source • n-Channel MOSFET and
• Diode p-Channel MOSFET2

• Switch • External I vs. U3

• Voltage-Controlled Voltage Source1 • External U vs. I3

• Voltage-Controlled Current Source1 • External I-Terminal3

• Current-Controlled Voltage Source1 • SPICE Circuit Import

1 • SPICE Circuit Export
• Current-Controlled Current Source
1
Selected from the Dependent Sources submenu when you right-click main node.
2
Selected from the Transistors submenu when you right-click main node.
3 Selected from the External Couplings submenu when you right-click main node.

Ground Node
The Ground Node ( ) feature adds a ground node with the default node number zero
to the electrical circuit. This is the default node in the Electrical Circuit interface. More

306 | CHAPTER 5: AC/DC INTERFACES

ground nodes can be added but those must have unique node numbers and are by
default given higher node numbers.

GROUND CONNECTION
Set the Node name for the ground node in the circuit. The convention is to use 0 (zero)
for the ground node. If adding more ground nodes, each must have a unique node
name (number).

Voltmeter
The Voltmeter ( ) feature connects a voltmeter (voltage measurement device)
between two nodes in the electrical circuit. A voltmeter behaves electrically as an open
circuit. The voltmeter node adds a Probe sampling the voltage across it.

NODE CONNECTIONS
Set the two Node names for the connecting nodes for the resistor.

Ampère Meter
The Ammeter ( ) feature connects an ammeter (current measurement device)
between two nodes in the electrical circuit. An ammeter behaves electrically as a short
circuit. The ammeter node adds a Probe sampling the current through it.

NODE CONNECTIONS
Set the two Node names for the connecting nodes for the resistor.

DEVICE PARAMETERS
Enter the Resistance of the resistor.

Resistor
The Resistor ( ) feature connects a resistor between two nodes in the electrical
circuit.

NODE CONNECTIONS
Set the two Node names for the connecting nodes for the resistor.

DEVICE PARAMETERS
Enter the Resistance of the resistor.

THE ELECTRICAL CIRCUIT INTERFACE | 307

 Capacitor
The Capacitor ( ) feature connects a capacitor between two nodes in the electrical
circuit.

NODE CONNECTIONS
Set the two Node names for the connecting nodes for the capacitor.

DEVICE PARAMETERS
Enter the Capacitance of the capacitor.

Inductor
The Inductor ( ) feature connects an inductor between two nodes in the electrical
circuit.

NODE CONNECTIONS
Set the two Node names for the connecting nodes for the inductor.

DEVICE PARAMETERS
Enter the Inductance of the inductor.

Voltage Source
The Voltage Source ( ) feature connects a voltage source between two nodes in the
electrical circuit.

NODE CONNECTIONS
Set the two Node names for the connecting nodes for the voltage source. The first node
represents the positive reference terminal.

DEVICE PARAMETERS
Enter the Source type that should be adapted to the selected study type. It can be
General source, AC-source, or a time-dependent Sine source or Pulse source. Depending
on the choice of source, also specify the following parameters:

• For a General source, the Voltage Vsrc (default value: 1 V). General sources are active
in Stationary, Time-Dependent and Frequency Domain studies.
• For an AC-source: the Voltage Vsrc (default value: 1 V) and the Phase Θ (default
value: 0 rad). AC-sources are active in Frequency Domain studies only.

308 | CHAPTER 5: AC/DC INTERFACES

• For a sine source: the Voltage Vsrc (default value: 1 V), the Offset Voff (default value:
0 V), the Frequency (default value: 1 kHz), and the Phase Θ (default value: 0 rad).
The sine sources are active in Time-Dependent studies and also in Stationary
studies, providing that a value for t has been provided as a model parameter or
global variable.
• For a pulse source: the Voltage Vsrc (default value: 1 V), the Offset Voff (default value:
0 V), the Delay td (default value: 0s), the Rise time tr and Fall time tf (default values:
0 s), the Pulse width pw (default value: 1 μs), and the Period Tper (default value: 2 μs).
The pulse sources are active in Time-Dependent studies and also in Stationary
studies, providing that a value for t has been provided as a model parameter or
global variable.

All values are peak values rather than RMS.

For the AC source, the frequency is a global input set by the solver. AC
sources should be used in Frequency-domain studies only. Do not use the
Sine source unless the model is time dependent.

Current Source
The Current Source ( ) feature connects a current source between two nodes in the
electrical circuit.

NODE CONNECTIONS
Set the two Node names for the connecting nodes for the current source. The first node
represents the positive reference terminal from where the current flows through the
source to the second node.

DEVICE PARAMETERS
Enter the Source type that should be adapted to the selected study type. It can be
General source, AC-source, or a time-dependent Sine source or Pulse source. Depending
on the choice of source, also specify the following parameters:

• For a General source, the Current isrc (default value: 1 A). General sources are active
in Stationary, Time-Dependent and Frequency Domain studies.
• For an AC-source: the Current isrc (default value: 1 A) and the Phase Θ (default
value: 0 rad). AC-sources are active in Frequency Domain studies only.

THE ELECTRICAL CIRCUIT INTERFACE | 309

 • For a sine source: the Current isrc (default value: 1 A), the Offset ioff (default value:
0 A), the Frequency (default value: 1 kHz), and the Phase Θ (default value: 0 rad).
The sine sources are active in Time-Dependent studies and also in Stationary
studies, providing that a value for t has been provided as a model parameter or
global variable.
• For a pulse source: the Current isrc (default value: 1 A), the Offset ioff (default value:
0 A), the Delay td (default value: 0 s), the Rise time tr and Fall time tf (default values:
0 s), the Pulse width pw (default value: 1 μs), and the Period Tper (default value: 2 μs).
The pulse sources are active in Time-Dependent studies and also in Stationary
studies, providing that a value for t has been provided as a model parameter or
global variable.

All values are peak values rather than RMS.

For the AC source, the frequency is a global input set by the solver. AC
sources should be used in frequency-domain studies only. Do not use the
Sine source unless the model is time dependent.

Voltage-Controlled Voltage Source

The Voltage-Controlled Voltage Source ( ) feature connects a voltage-controlled
voltage source between two nodes in the electrical circuit. A second pair of nodes
define the input control voltage.

NODE CONNECTIONS
Specify four Node names: the first pair for the connection nodes for the voltage source
and the second pair defining the input control voltage. The first node in a pair
represents the positive reference terminal.

DEVICE PARAMETERS
There are two options to define the relationship between the control voltage and
resulting voltage. The Use gain method defines the resulting voltage to be the control
voltage multiplied by the gain. The Custom expression method can define the
relationship with an arbitrary expression.

310 | CHAPTER 5: AC/DC INTERFACES

Voltage-Controlled Current Source
The Voltage-Controlled Current Source ( ) feature connects a voltage-controlled
current source between two nodes in the electrical circuit. A second pair of nodes
define the input control voltage.

NODE CONNECTIONS
Specify four Node names: the first pair for the connection nodes for the current source
and the second pair defining the input control voltage. The first node in a pair
represents the positive voltage reference terminal or the one from where the current
flows through the source to the second node.

DEVICE PARAMETERS
There are two options to define the relationship between the control voltage and
resulting current. The Use gain method defines the resulting current to be the control
voltage multiplied by the gain (SI units: S). The Custom expression method can define
the relationship with an arbitrary expression.

Current-Controlled Voltage Source

The Current-Controlled Voltage Source ( ) feature connects a current-controlled
voltage source between two nodes in the electrical circuit. The input control current
is the one flowing through a two-pin device.

NODE CONNECTIONS
Set two Node names for the connection nodes for the voltage source. The first node in
a pair represents the positive reference terminal.

DEVICE PARAMETERS
There are two options to define the relationship between the control current and
resulting voltage. The Use gain method defines the resulting voltage to be the control
current multiplied by the gain (SI units: Ω). The Custom expression method can define
the relationship with an arbitrary expression.

Current-Controlled Current Source

The Current-Controlled Current Source ( ) feature connects a current-controlled
current source between two nodes in the electrical circuit. The input control current
is the one flowing through a named device that must be a two-pin device.

THE ELECTRICAL CIRCUIT INTERFACE | 311

 NODE CONNECTIONS
Specify two Node names for the connection nodes for the current source. The first node
in a pair represents the positive reference terminal from where the current flows
through the source to the second node.

DEVICE PARAMETERS
There are two options to define the relationship between the control current and
resulting current. The Use gain method defines the resulting current to be the control
current multiplied by the gain. The Custom expression method can define the
relationship with an arbitrary expression.

Switch
The Switch ( ) feature is used to connect or disconnect the conducting path in a
circuit under specific conditions.

NODE CONNECTIONS
Specify two Node names for the connection nodes for the current source. The first node
in a pair represents the positive reference terminal from where the current flows
through the source to the second node.

SWITCH CONDITIONS
There are three types of conditions, Voltage controlled, Current controlled, and Custom
expressions. For each type of condition there are two conditions, one for turn on and
one for turn off. The on condition is true if the On condition expression is larger than
zero, while the off condition is true if the Off condition is less than zero.

The Initial state list has three options, Use on condition, Use off condition, and Boolean
expression. The two former options mean that the switch will have an initial state
matching to the on or off condition. The third option makes the switch's initial state
match a custom Boolean expression. Separating on, off, and initial states makes the
switch more flexible and can support Schmitt-trigger style switches and various latches.

For the Voltage controlled switch, it is necessary to specify two nodes that defines the
voltage sens.v that the switch state depends on. The conditions must be written as a
function of this variable. Similarly, for the Current controlled switch it is necessary to
specify a two-pin device that defines the current sens.i that the switch state depends
on.

312 | CHAPTER 5: AC/DC INTERFACES

SWITCH PARAMETERS
When the switch is in the on state it has a non-zero resistance specified by the On
resistance expression. For the off state no current flows through the switch (infinite
resistance). There is also a transition time for the switch to turn on and off set by the
Switching time expression. The switch triggers an implicit event that updates a discrete
state variable (with suffix _state).

Subcircuit Definition
The Subcircuit Definition ( ) feature is used to define subcircuits, which can be
inserted as devices into the main circuit using Subcircuit Instance nodes. Create the
subcircuit by adding subnodes to the Subcircuit Definition node, either by using the
Physics toolbar, or by right-clicking the Subcircuit Definition.

SUBCIRCUIT PINS
Define the Pin names at which the subcircuit connects to the main circuit or to other
subcircuits when referenced by a Subcircuit Instance node. The Pin names refer to
circuit nodes in the subcircuit. The order in which the Pin names are defined is the
order in which they are referenced by a Subcircuit Instance node. The devices
constituting the subcircuit should be connected only to the subcircuit’s pins and to
themselves.

INPUT PARAMETERS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options. Specify input parameters to a subcircuit that can be changed from a
subcircuit instance. These input parameters can be used in all expression-style edit
fields that affect the parameters of a device, for example, resistance, capacitance, and
current gain. In this way, a subcircuit can represent a parameterized custom device
model.

Subcircuit Instance
The Subcircuit Instance ( ) feature represents an instance of a subcircuits defined by
a Subcircuit Definition feature.

NODE CONNECTIONS
Select the Name of subcircuit link from the list of defined subcircuits in the circuit model
and the circuit Node names at which the subcircuit instance connects to the main circuit
or to another subcircuit if used therein.

THE ELECTRICAL CIRCUIT INTERFACE | 313

 INPUT PARAMETERS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options. Specify input parameters to a subcircuit that can be changed from a
subcircuit instance. These input parameters can be used in all expression-style edit
fields that affect the parameters of a device, for example, resistance, capacitance, and
current gain. In this way, a subcircuit can represent a parameterized custom device
model.

NPN BJT and PNP BJT

The NPN BJT ( ) and the PNP BJT ( ) device models are large-signal models for
bipolar junction transistors (BJT). It is an advanced device model and no thorough
description and motivation of the many input parameters are attempted here. Many
device manufacturers provide model input parameters for this BJT model. For any
particular make of BJT, the device manufacturer should be the primary source of
information.

NODE CONNECTIONS
Specify three Node names for the connection nodes for the BJT device. These represent
the collector, base, and emitter nodes for the NPN transistor, and the emitter, base, and
collector nodes for the PNP transistor.

MODEL PARAMETERS
Specify the Model Parameters. Reasonable defaults are provided but for any particular
BJT, the device manufacturer should be the primary source of information.

The interested reader is referred to Ref. 1 for more details on

semiconductor modeling within circuits.

For an explanation of the Model Parameters see Bipolar Transistors.

n-Channel MOSFET and p-Channel MOSFET

The n-Channel MOSFET ( ) and the p-Channel MOSFET ( ) device models are
large-signal models for, respectively, an n-Channel MOS field-effect transistor
(MOSFET) and p-Channel MOSFET. These are advanced device models and no
thorough description and motivation of the many input parameters are attempted
here. Many device manufacturers provide model parameters for the MOSFET models.

314 | CHAPTER 5: AC/DC INTERFACES

For any particular make of MOSFET, the device manufacturer should be the primary
source of information.

NODE CONNECTIONS
Specify four Node names for the connection nodes for the n-Channel MOSFET or
p-Channel MOSFET device. These represent the drain, gate, source, and bulk nodes,
respectively.

MODEL PARAMETERS
Specify the Model Parameters. Reasonable defaults are provided but for any particular
MOSFET, the device manufacturer should be the primary source of information.

The interested reader is referred to for more details on semiconductor

modeling within circuits.

For an explanation of the Model Parameters see MOSFET Transistors.

Mutual Inductance
The Mutual Inductance allows specifying a coupling between two existing Inductor
features in the circuit. The mutual inductance of the coupling is

M = k L1 L2

where k is the coupling factor and L1 and L2 are the inductances of the inductors.

DEVICE PARAMETERS
Enter values or expressions for the:

• Coupling factor k (dimensionless). The value must be between 0 and 1, and the
default is 0.98.
• First inductance L1 (SI unit: H) and Second inductance L2 (SI unit: H). These must
be set to two different Inductor features in the circuit.

Transformer
The Transformer feature represents either a combination of two Inductor and a Mutual
Inductance features, or an ideal transformer.

THE ELECTRICAL CIRCUIT INTERFACE | 315

 NODE CONNECTIONS
Enter or edit the table in the Node names column for the primary and secondary node
connections.

DEVICE PARAMETERS
Choose a Transformer model — Specify inductors (the default) or Ideal transformer.

For Specify inductors enter values or expressions for the:

• Coupling factor k (dimensionless). The default is 0.98.

• First inductance L1 (SI unit: H). The default is 1 mH.
• Second inductance L2 (SI unit: H). The default is 1 mH.

For Ideal transformer enter values or expressions for the Winding ratio N1/N2
(dimensionless). The default is 10.

Battery Open Circuit Voltage

The Battery Open Circuit Voltage node defines a voltage source in the circuit that
depends on the state-of-charge of a battery. In time-dependent simulations the
state-of-charge is calculated by integrating the current passing through the circuit
element, using the Battery cell capacity and Initial state-of-charge parameters.

Use the table in the Open Circuit Voltage section to define how the voltage depends on
the state-of-charge.

The Temperature derivative of open circuit settings may be used to define a

temperature-dependent open circuit voltage, and an reversible (entropic) heat source.

Resistor-Capacitor Couple
The Resistor-Capacitor Couple node defines a resistor and capacitor coupled in parallel.
The device model has two modes of operation which are using either the Resistance
and capacitance values or the Resistance and time-constant values as input.

NODE CONNECTIONS
Specify two Node names for the positive and negative nodes for the Resistor-capacitor
couple device.

316 | CHAPTER 5: AC/DC INTERFACES

Diode
The Diode device model ( ) is a large-signal model for a diode. It is an advanced
device model and no thorough description and motivation of the many input
parameters are attempted here. The interested reader is referred to for more details on
semiconductor modeling within circuits. Many device manufacturers provide model
parameters for this diode model. For any particular make of diode, the device
manufacturer should be the primary source of information.

NODE CONNECTIONS
Specify two Node names for the positive and negative nodes for the Diode device.

MODEL PARAMETERS
Specify the Model Parameters. Reasonable defaults are provided but for any particular
diode, the device manufacturer should be the primary source of information.

For an explanation of the Model Parameters see Diode.

External I vs. U
The External I vs. U ( ) feature connects an arbitrary voltage measurement (for
example, a circuit terminal or circuit port boundary or a coil domain from another
physics interface) as a voltage source between two nodes in the electrical circuit. The
resulting circuit current from the first node to the second node is typically coupled
back as a prescribed current source in the context of the voltage measurement.

NODE CONNECTIONS
Specify the two Node names for the connecting nodes for the voltage source. The first
node represents the positive reference terminal.

EXTERNAL DEVICE
Enter the source of the Voltage. If circuit or current excited terminals or circuit ports
are defined on boundaries or domains or a multiturn coil domains is defined in other
physics interfaces, these display as options in the Voltage list. Also select the User defined
option and enter your own voltage variable, for example, using a suitable coupling
operator. For inductive or electromagnetic wave propagation models, the voltage
measurement must be performed as an integral of the electric field because the electric

THE ELECTRICAL CIRCUIT INTERFACE | 317

 potential only does not capture induced EMF. Also the integration must be performed
over a distance that is short compared to the local wavelength.

Except when coupling to a circuit terminal, circuit port, or coil, the

current flow variable must be manually coupled back in the electrical
circuit to the context of the voltage measurement. This applies also when
coupling to a current excited terminal. The name of this current variable
follows the convention cirn.IvsUm_i, where cirn is the tag of the
Electrical Circuit interface node and IvsUm is the tag of the External I vs.
U node. The tags are typically displayed within curly brackets {} in the
Model Builder.

Nonlocal Couplings and Coupling Operators in the COMSOL

Multiphysics Reference Manual

External U vs. I
The External U vs. I ( ) feature connects an arbitrary current measurement (for
example, a coil domain from another physics interface) as a current source between
two nodes in the electrical circuit. The resulting circuit voltage between the first node
and the second node is typically coupled back as a prescribed voltage source in the
context of the current measurement.

NODE CONNECTIONS
Specify the two Node names for the connecting nodes for the current source. The
current flows from the first node to the second node.

EXTERNAL DEVICE
Enter the source of the Current. Voltage excited terminals or lumped ports defined on
boundaries in other physics interfaces are natural candidates but do not appear as
options in the Voltage list because those do not have an accurate built-in current

318 | CHAPTER 5: AC/DC INTERFACES

measurement variable. A User defined option must be selected and a current variable
entered, for example, using a suitable coupling operator.

The voltage variable must be manually coupled back in the electrical

circuit to the context of the current measurement. This applies also when
coupling to a voltage excited terminal or lumped port. The name of this
voltage variable follows the convention cirn.UvsIm_v, where cirn is the
tag of the Electrical Circuit interface node and UvsIm is the tag of the
External U vs. I node. The tags are typically displayed within curly
brackets {} in the Model Builder.

Nonlocal Couplings and Coupling Operators in the COMSOL

Multiphysics Reference Manual

External I-Terminal
The External I-Terminal ( ) feature connects an arbitrary voltage-to-ground
measurement (for example, a circuit terminal from another physics interface) as a
voltage-to-ground assignment to a node in the electrical circuit. The resulting circuit
current from the node is typically coupled back as a prescribed current source in the
context of the voltage measurement. This node does not apply when coupling to
inductive or electromagnetic wave propagation models because then voltage must be
defined as a line integral between two points rather than a single point measurement
of electric potential. For such couplings, use the External I vs. U node instead.

NODE CONNECTIONS
Set the Node name for the connecting node for the voltage assignment.

EXTERNAL TERMINAL
Enter the source of the Voltage. If circuit- or current-excited terminals are defined on
boundaries in other physics interfaces, these display as options in the Voltage list. Also

THE ELECTRICAL CIRCUIT INTERFACE | 319

 select the User defined option and enter a voltage variable, for example, using a suitable
coupling operator.

• Except when coupling to a circuit terminal, the current flow variable

must be manually coupled back in the electrical circuit to the context
of the voltage measurement. This applies also when coupling to a
current excited terminal. The name of this current variable follows the
convention cirn.termIm_i, where cirn is the tag of the Electrical
Circuit interface node and termIm is the tag of the External I-Terminal
node. The tags are typically displayed within curly brackets {} in the
Model Builder.
• When connecting the finite element model between two circuit nodes
that both are not grounded, the External I-Terminal node cannot be
used. In this case, use External I vs. U or External U vs. I instead.

Nonlocal Couplings and Coupling Operators in the COMSOL

Multiphysics Reference Manual.

SPICE Circuit Import

Right-click the Electrical Circuit ( ) feature node to import an existing SPICE netlist
(select Import Spice Netlist). A window opens — enter a file location or browse your
directories to find one. The default file extension for a SPICE netlist is .cir. The
SPICE circuit import translates the imported netlist into Electrical Circuit interface
nodes so these define the subset of SPICE features that can be imported.

See SPICE Import and Export about the supported SPICE commands.

SPICE Circuit Export

Right-click the Electrical Circuit ( ) feature node to export the current circuit to the
SPICE netlist file format (select Export Spice Netlist ). A window opens — enter a

320 | CHAPTER 5: AC/DC INTERFACES

file location or browse your directories to find one. The default file extension for a
SPICE netlist is .cir. The compatible circuit nodes are exported as SPICE devices

See SPICE Circuit Export for more details on the supported SPICE
commands.

THE ELECTRICAL CIRCUIT INTERFACE | 321

 Theory for the Electrostatics
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 = σE

the equation of continuity

∂-----
ρ-
+ ∇ ⋅ Jc = 0
∂t

and Gauss’ law

∇ ⋅ ( εE ) = ρ

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

322 | CHAPTER 5: AC/DC INTERFACES

 ∂-----
ρ- σ
+ --- ρ = 0
∂t ε

This equation has the solution

–t ⁄ τ
ρ ( t ) = ρ0 e

where

ε
τ = ---
σ

is called the charge relaxation time. For a good conductor like copper, τ 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 5-3 below,
TABLE 5-3: SUITABLE PHYSICS INTERFACE AND STUDY TYPE FOR DIFFERENT TIME-SCALE REGIMES.

CASE PHYSICS INTERFACE STUDY TYPE

τ>>t Electrostatics Stationary

τ<<t Electric Currents Stationary
τ~ t Electric Currents Time Dependent or Frequency Domain

FIRST CASE: τ >> 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 = ε0E
+ P between D and E, you can rewrite Gauss’ law as a variant of Poisson’s equation

– ∇ ⋅ ( ε 0 ∇V – P ) = ρ

THEORY FOR THE ELECTROSTATICS INTERFACE | 323

 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: τ <<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 = σE + J e

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

∇ ⋅ J c = – ∇ ⋅ ( σ ∇V – J e ) = 0

To handle current sources, the equation can be generalized to

– ∇ ⋅ ( σ ∇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 = ε0E + P between the
electric displacement D and the electric field E, it is possible to represent Gauss’ law
as the following equation:

– ∇ ⋅ ( ε 0 ∇V – P ) = ρ

324 | CHAPTER 5: AC/DC INTERFACES

In this equation, the physical constant, ε0 (SI unit: F/m) is the permittivity of vacuum,
P (SI unit: C/m2) is the electric polarization vector, and ρ (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 ( ε 0 ∇V – P ) = ρ

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 ϕ 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.

THEORY FOR THE ELECTROSTATICS INTERFACE | 325

 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, conductors 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 .

The Electric Currents Interface assumes that there is only one type of charge carrier.
When there are multiple charge carriers, it is often necessary to solve the transport
equation for each charge carrier as well as the Poisson’s equation with Electrostatics
interface.

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 = σE + J e

where σ 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 = – ∇ ⋅ ( σ ∇V – J e ) = 0

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

– ∇ ⋅ ( σ ∇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:

326 | CHAPTER 5: AC/DC INTERFACES

 – ∇ ⋅ d ( σ ∇V – J e ) = dQ j (5-1)

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 ϕ direction, which implies that the electric field is tangential to the rz-plane.

THEORY FOR THE ELECTRIC CURRENTS INTERFACE | 327

 Theory for the Electrical Circuit
Interface
The Electrical Circuit Interface theory is discussed in this section:

• Electric Circuit Modeling and the Semiconductor Device Models

• Bipolar Transistors
• MOSFET Transistors
• Diode
• Reference for the Electrical Circuit Interface

Connecting to Electrical Circuits

Electric Circuit Modeling and the Semiconductor Device Models

Electrical circuit modeling capabilities are useful when simulating all sorts of electrical
and electromechanical devices ranging from heaters and motors to advanced plasma
reactors in the semiconductor industry. There are two fundamental ways that an
electrical circuit model relates to a physical field model.

• The field model is used to get a better, more accurate description of a single device
in the electrical circuit model.
• The electrical circuit is used to drive or terminate the device in the field model in
such a way that it makes more sense to simulate both as a tightly coupled system.

The Electrical Circuit interface makes it possible to add nodes representing circuit
elements directly to the Model Builder tree in a COMSOL Multiphysics model. The
circuit variables can then be connected to a physical device model to perform
co-simulations of circuits and multiphysics. The model acts as a device connected to
the circuit so that its behavior is analyzed in larger systems.

The fundamental equations solved by the Electrical Circuit interface are Kirchhoff’s
circuit laws, which in turn can be deduced from Maxwell’s equations. The supported
study types are Stationary, Frequency Domain, and Time Dependent.

328 | CHAPTER 5: AC/DC INTERFACES

There are three more advanced large-signal semiconductor device features available in
the Electrical Circuit interface. The equivalent circuits and the equations defining their
non-ideal circuit elements are described in this section. For a more complete treatise
on semiconductor device modeling see Ref. 1.

Bipolar Transistors
Figure 5-1 illustrates the equivalent circuit for the npn bipolar junction transistor.

Figure 5-1: A circuit for the bipolar transistor.

The pnp transistor model is similar in all regards to the npn transistor, with the
difference that the polarities of the currents and voltages involved are reversed. The
following equations are used to compute the relations between currents and voltages
in the circuit.

THEORY FOR THE ELECTRICAL CIRCUIT INTERFACE | 329

 R B – R BM
v rb = ----  R BM – -------------------------- i b
1
A f bq 

 v be
 --------------
v bc
--------------  
  – 1
NF VT NR VT
= -----------------------------------------------  1 + 1 + 4I S  ----------------------- + ------------------------ 
1 e –1 e
f bq
v bc v be  I KF A I KR A 
2  1 – ----------- – -----------    
 V AF V AR 
v be v be
 I S  -------------
N V
-   --------------
N V 
i be = A  -------  e F T – 1 + I SE  e E T – 1 
 BF    
v bc v bc
 I S  --------------
N V   --------------
N V 
i bc = A  --------  e R T – 1 + I SC  e C T – 1 
B
 R   
v be v bc
 I S  -------------
N V
- --------------
N V 
i ce = A  -------  e F T + e C T 
f
 bq  
k B T NOM
V T = ------------------------
q

There are also two capacitances that use the same formula as the junction capacitance
of the diode model. In the parameter names below, replace x with C for the
base-collector capacitance and E for the base-emitter capacitance.

 v bx  – MJx
 1 – ---------
 -
 V Jx v bx < F C V Jx
C jbx 
= AC Jx × 
v bx  v bx ≥ F C V Jx
 ( 1 – F ) – 1 – M Jx  1 – F ( 1 + M ) + M ---------
-
 C  C Jx Jx V 
Jx

The model parameters are listed in the table below.

TABLE 5-1: BIPOLAR TRANSISTOR MODEL PARAMETERS.

PARAMETER DEFAULT DESCRIPTION

BF 100 Ideal forward current gain

BR 1 Ideal reverse current gain
2
CJC 0 F/m Base-collector zero-bias depletion capacitance
CJE 0 F/m2 Base-emitter zero-bias depletion capacitance
FC 0.5 Breakdown current
2
IKF Inf (A/m ) Corner for forward high-current roll-off

330 | CHAPTER 5: AC/DC INTERFACES

TABLE 5-1: BIPOLAR TRANSISTOR MODEL PARAMETERS.

PARAMETER DEFAULT DESCRIPTION

IKR Inf (A/m2) Corner for reverse high-current roll-off

IS 10-15 A/m2 Saturation current
ISC 0 A/m2 Base-collector leakage saturation current
ISE 0 A/m2 Base-emitter leakage saturation current
MJC 1/3 Base-collector grading coefficient
MJE 1/3 Base-emitter grading coefficient
NC 2 Base-collector ideality factor
NE 1.4 Base-emitter ideality factor
NF 1 Forward ideality factor
NR 1 Reverse ideality factor
RB 0 Ω⋅m2 Base resistance
RBM 0 Ω⋅m2 Minimum base resistance
RC 0 Ω⋅m2 Collector resistance
RE 0 Ω⋅m2 Emitter resistance
TNOM 298.15 K Device temperature
VAF Inf (V) Forward Early voltage
VAR Inf (V) Reverse Early voltage
VJC 0.71 V Base-collector built-in potential
VJE 0.71 V Base-emitter built-in potential

THEORY FOR THE ELECTRICAL CIRCUIT INTERFACE | 331

 MOSFET Transistors
Figure 5-2 illustrates an equivalent circuit for the n-channel MOSFET transistor. The
p-channel MOSFET transistor is treated similarly, but the polarities of the involved
voltages are reversed.

Figure 5-2: A circuit for the MOSFET transistor.

The following equations are used to compute the relations between currents and
voltages in the circuit.

332 | CHAPTER 5: AC/DC INTERFACES

  KP
 W - -------
 ----
L 2
( 1 + Λv ds )v ds ( 2v th – v ds ) v ds < v th

i ds =  W KP 2
 ----- ------- ( 1 + Λv ds )v th v ds ≥ v th
 L 2
 0 v ds < v th ≤ 0

v th = v gs – ( V TO + Γ ( Φ – v bs – Φ ) )
v bd
 -----------
NV
- 
i bd = I S  e T – 1
 
v bs
 -----------
NV
- 
i bs = I S  e T – 1
 
k B T NOM
V T = ------------------------
q

There are also several capacitances between the terminals

C gd = C gd0 W
C gs = C gs0 W

1 – v
–M J
 bd
--------
-
  PB  v bx < F C P B
C jbd = C BD × 
v bx v bx ≥ F C P B
 ( 1 – F ) – 1 – M J  1 – F ( 1 + M ) + M -------
-
 C  C J J PB 

The model parameters are as follows:

TABLE 5-2: MOSFET TRANSISTOR MODEL PARAMETERS.

PARAMETER DEFAULT DESCRIPTION

CBD 0 F/m Bulk-drain zero-bias capacitance

CGDO 0 F/m Gate-drain overlap capacitance
CGSO 0 F/m Gate-source overlap capacitance
FC 0.5 Capacitance factor
IS 1e-13 A Bulk junction saturation current
KP 2e-5 A/V2 Transconductance parameter
L 50e-6 m Gate length
MJ 0.5 Bulk junction grading coefficient

THEORY FOR THE ELECTRICAL CIRCUIT INTERFACE | 333

 TABLE 5-2: MOSFET TRANSISTOR MODEL PARAMETERS.

PARAMETER DEFAULT DESCRIPTION

N 1 Bulk junction ideality factor

PB 0.75 V Bulk junction potential
RB 0Ω Bulk resistance
RD 0Ω Drain resistance
RDS Inf (Ω) Drain-source resistance
RG 0Ω Gate resistance
RS 0Ω Source resistance
TNOM 298.15 K Device temperature
VTO 0V Zero-bias threshold voltage
W 50e-6 m Gate width
Γ (GAMMA) 1 V0.5 Bulk threshold parameter
Φ (PHI) 0.5 V Surface potential
Λ (LAMBDA) 0 1/V Channel-length modulation

334 | CHAPTER 5: AC/DC INTERFACES

Diode
Figure 5-3 illustrates equivalent circuit for the diode.

Figure 5-3: A circuit for the diode.

The following equations are used to compute the relations between currents and
voltages in the circuit.

THEORY FOR THE ELECTRICAL CIRCUIT INTERFACE | 335

 i d = i dhl + i drec + i db + i c
vd
 -----------
NV
-
 1
i dhl = I S  e T – 1 ---------------------------------------------------
  vd
I S  -----------
NV T
-

1 + ---------  e – 1
I KF  
vd
 --------------
N V 
i drec = I SR  e R T – 1
 
vd + BV
– -----------------
-
N BV V T
i db = I BV e

 vd  –M
  1 – ------
- vd < FC VJ
  V J
C j = C J0 × 
 – 1 – M vd
 ( 1 – FC )  1 – F C ( 1 + M ) + M ------- v d ≥ F C V J
 VJ

k B T NOM
V T = ------------------------
q

where the following model parameters are required.

TABLE 5-3: DIODE TRANSISTOR MODEL PARAMETERS.

PARAMETER DEFAULT DESCRIPTION

BV Inf (V) Reverse breakdown voltage

CJ0 0F Zero-bias junction capacitance
FC 0.5 Forward-bias capacitance coefficient
IBV 1e-09 A Current at breakdown voltage
IKF Inf (A) Corner for high-current roll-off
IS 1e-13 A Saturation current
M 0.5 Grading coefficient
N 1 Ideality factor
NBV 1 Breakdown ideality factor
NR 2 Recombination ideality factor
RS 0Ω Series resistance
TNOM 298.15 K Device temperature
VJ 1.0 V Junction potential

336 | CHAPTER 5: AC/DC INTERFACES

Reference for the Electrical Circuit Interface
1. P. Antognetti and G. Massobrio, Semiconductor Device Modeling with Spice, 2nd
ed., McGraw-Hill, 1993.

THEORY FOR THE ELECTRICAL CIRCUIT INTERFACE | 337

338 | CHAPTER 5: AC/DC 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 Diluted Species in Porous Media Interface
• The Transport of Diluted Species in Fractures Interface
• The Transport of Concentrated Species Interface
• The Transport of Concentrated Species in Porous Media 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 Nonisothermal Reacting Flow Multiphysics Interfaces

The theory for all the interfaces is also discussed at the end of the chapter and links
are included with the interfaces.

339
 T he T r a ns po r t of D i l u t ed Sp eci es
Interface
The Transport of Diluted Species (tds) interface ( ), found under the Chemical Species
Transport branch ( ), is used to calculate the concentration field of a dilute solute in
a solvent. Transport and reactions of the species dissolved in a gas, liquid, or solid can
be handled with this interface. The driving forces for transport can be diffusion by
Fick’s law, convection when coupled to a flow field, and migration, when coupled to
an electric field.

The interface supports simulation of transport by convection and diffusion in 1D, 2D,
and 3D as well as for axisymmetric components in 1D and 2D. The dependent variable
is the molar concentration, c. Modeling multiple species transport is possible, whereby
the physics interface solves for the molar concentration, ci, of each species i.

SETTINGS
The Label is the default physics interface name.

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

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

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

OUT-OF-PLANE THICKNESS
For 2D components, the Thickness field (default value: 1 m) defines a parameter for the
thickness of the geometry perpendicular to the two-dimensional cross-section. Both
constant and varying thicknesses are supported. The value of this parameter is used,
among other things, to automatically calculate molar flow rates from the total molar
flux.

340 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

CROSS-SECTIONAL AREA
For 1D components, enter a Cross-sectional area Ac (SI unit: m2) to define a parameter
for the area of the geometry perpendicular to the 1D component. Both constant and
varying areas are supported. The value of this parameter is used, among other things,
to automatically calculate molar flow rates from the total molar flux. The default is 1
m2.

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

Note: Some of the additional transport mechanisms listed below are only available in
certain products. For details see 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 | 341

 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. Its 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

342 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

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 selected. 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 | 343

 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

344 | 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

Domain, Boundary, and Pair Nodes for the Transport of Diluted

Species Interface
The Transport of Diluted Species Interface has the following domain, boundary, point,
and pair nodes, listed in alphabetical order, available from the Physics ribbon toolbar

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 345

 (Windows users), Physics context menu (Mac or Linux users), or by right-clicking to
access the context menu (all users).

• To add a node, go to the Physics toolbar, no matter what operating

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

346 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

• Adsorption • Periodic Condition
• Concentration • Point Mass Source
• Continuity on Interior Boundaries • Porous Matrix
• Dispersion • Porous Medium
• Electrode Surface Coupling • Porous Electrode Coupling
• Equilibrium Reaction • Reaction Coefficients
• Fast Irreversible Surface Reaction • Reactions
• Fluid • Species Properties
• 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 • Unsaturated Porous Medium
• Mass-Based Concentrations • Volatilization
• No Flux
• Open Boundary
• Out-of-Plane Flux
• 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 | 347

 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.

Prescribing Conditions on Fluid-Solid Interfaces

Defining conditions on interfaces between different phases, typically a wall in contact
with a fluid, it is worthwhile to be careful with how variables in the conditions are
evaluated. COMSOL Multiphysics supports that variables are defined differently on
adjacent domains (or any other geometry dimension). Evaluating a variable with
differing definitions, the mean value is returned on a boundary separating the different
domains. The density, pressure, or temperature are examples of variables that may
differ in a fluid and a solid. In order to specify on which side a variable is evaluated, the
up and down operators (described in the COMSOL Multiphysics Reference Manual)
can be used.

Species Properties
Use this node to define parameters specific to each of the species. It is available when
the Migration in electric field check box is selected in the Transport Mechanisms section
of the interface.

The node will change its label depending on what inputs are available in the node. If
only Charge is available, it will be labeled “Species charges”.

CHARGE
Enter the charge number zc (dimensionless, but requires a plus or minus sign) for each
species.

ACTIVITY
This section is available when the Species Activity combo box is set to Debye-Hückel or
User defined.

If Debye-Hückel is selected, enter the ion size number, a0, for each species. If User
defined is selected, enter the activity coefficient, f, for each species.

348 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Transport Properties
The settings in this node are dependent on the check boxes selected under Transport
Mechanisms on the Settings window for the Transport of Diluted Species interface. It
includes only the sections required by the activated transport mechanisms. It has all the
equations defining transport of diluted species as well as inputs for the material
properties.

MODEL INPUTS
The temperature model input is always available. Select the source of the Temperature.
For User defined, enter a value or expression for the temperature in the input field. This
input option is always available.

You can also select the temperature solved for by a Heat Transfer interface added to
the model component. These physics interfaces are available for selection in the
Temperature list.

CONVECTION
If transport by convection is active, the velocity field of the solvent needs to be
specified. Select the source of the Velocity field. For User defined, enter values or
expressions for the velocity components in the input fields. This input option is always
available.

You can also select the velocity field solved for by a Fluid Flow interface added to the
model component. These physics interfaces are available for selection in the Velocity
field list.

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

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

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

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 349

 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 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/.

350 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

Initial Values
The Initial Values node specifies the initial values for the concentration of each species.
These serve as an initial guess for a stationary solver or as initial conditions for a
transient simulation.

DOMAIN SELECTION
If there are several types of domains with different initial values defined, it might be
necessary to remove some domains from the selection. These are then defined in an
additional Initial Values node.

INITIAL VALUES
Enter a value or expression for the initial value of the Concentration or concentrations,
ci. This also serves as a starting guess for stationary problems.

Mass-Based Concentrations
Use the Mass-Based Concentrations node to add postprocessing variables for mass-based
concentrations (SI unit: kg/m3) and mass fractions (dimensionless) for all species.

MIXTURE PROPERTIES
The default Solvent density ρsolvent is taken From material. For User defined, enter a
value or expression manually. Define the Molar mass of each species, which is needed
to calculate the mass-based concentration.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 351

 Reactions
Use the Reactions node to account for the consumption or production of species
through chemical reactions. Define the rate expressions as required.

DOMAIN SELECTION
From the Selection list, choose the domains on which to define rate expression or
expressions that govern the source term in the transport equations.

Several reaction nodes can be used to account for different reactions in different parts
for the modeling geometry.

REACTION RATES
Add a rate expression Ri (SI unit: mol/(m3·s)) for species i. Enter a value or expression
in the field. Note that if you have the Chemistry interface available, provided with the
Chemical Reaction Engineering Module, the reaction rate expressions can be
automatically generated and picked up using the drop-down list. 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 in the case of using the
volume of a particular phase (applicable when modeling an unsaturated porous
medium).

• For Total volume, the reaction expressions, in mol/(m3·s), are specified per unit
volume of the model domain (multiplied by unity).
• For Pore volume, the reaction expressions, in mol/(m3·s), are specified per unit
volume of total pore space. The reaction expressions will be multiplied by the
domain porosity, εp. (εp equals unity for nonporous domains).
• For Liquid phase, the reaction expressions, in mol/(m3·s), are specified per unit
volume of liquid in the pore space. The expressions will be multiplied by the liquid
volume fraction θl. (θl equals the porosity (εp) on Porous Medium domains).
• For Gas phase, the reaction expressions, in mol/(m3·s), are multiplied by the gas
volume fraction θg = εp − θl. θg equals 0 for Porous Medium domains.

352 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

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

– n ⋅ ( – D∇c ) = 0

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

– n ⋅ ( – D∇c – zu m Fc∇φ ) = 0

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

When including the convection, the no flux condition prescribed is

– n ⋅ ( – D∇c + uc ) = 0

or

– n ⋅ ( – D∇c – zu m Fc∇φ + uc ) = 0

when migration of ionic species is included.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 353

 Inflow
Use this node to specify all species concentrations at an inlet boundary.

If you want to specify the concentration of a subset of the partaking species, this can
be done by using the Concentration node instead.

For the Electroanalysis interface, this node is available when you select the Convection
check box on the physics interface Settings window.

CONCENTRATION
For the concentration of each species c0,c (SI unit: mol/m3), enter a value or
expression.

BOUNDARY CONDITION TYPE

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

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

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.
You can find details about the different constraint settings in the section Constraint
Reaction Terms in the COMSOL Multiphysics Reference Manual.

FURTHER READING
See the theory chapter in the section Danckwerts Inflow Boundary Condition.

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:

354 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 n ⋅ ( – D ∇c ) = 0

Note that the Convection or the Migration in electric field transport mechanisms needs
to be included for this node to be available.

Concentration
This condition node adds a boundary condition for the species concentration. For
example, a c = c0 condition specifies the concentration of species c.

CONCENTRATION
Individually specify the concentration for each species. Select the check box for the
Species to specify the concentration, and then enter a value or expression in the
corresponding field. To use another boundary condition for a specific species, click to
clear the check box for the concentration of that species.

When defining conditions on boundaries between different phases, see the section
Prescribing Conditions on Fluid-Solid Interfaces.

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∇φ ) = J 0

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 355

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

When defining conditions on boundaries between different phases, see the section
Prescribing Conditions on Fluid-Solid Interfaces.

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

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

– n ⋅ ( – D∇c + uc ) = J 0

or

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

when migration of ionic species is included.

INWARD FLUX
Select the Species check box for the species for which to specify the flux, and enter a
value or expression for the inward flux in the corresponding field. Use a minus sign
when specifying a flux directed out of the system. To use another boundary condition
for a specific species, click to clear the check box for that species.

External convection
Set Flux type to External convection to prescribe a flux to or from an exterior domain
(not modeled) assumed to include convection. The exterior can for example include a
forced convection to control the temperature or to increase the mass transport. In this
case the prescribed mass flux corresponds to

J0 = kc ( cb – c )

where kc is a mass transfer coefficient and cb is the bulk concentration, the typical
concentration far into the surrounding exterior domain.

356 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Symmetry
The Symmetry node can be used to represent boundaries where the species
concentration is symmetric, that is, where there is no mass flux across the boundary.

This boundary condition is identical to that of the No Flux node.

Flux Discontinuity
This node represents a discontinuity in the mass flux across an interior boundary:

– n ⋅ [ ( J + uc ) u – ( J + uc ) d ] = N 0 J = – D∇c – zu m Fc∇φ

where the value N0 (SI unit: mol/(m2·s)) specifies the jump in total flux at the
boundary. This can be used to model a boundary source, for example a surface
reaction, adsorption or desorption.

FLUX DISCONTINUITY
In this section the jump in species flux (or surface source) is specified.

Select the Species check box for the species to specify and enter a value or expression
for the material flux jump in the corresponding field. To use a different boundary
condition for a specific species, click to clear the check box for the flux discontinuity
of that species.

Partition Condition
The Partition Condition node can be used to prescribe the relation between the
concentration of a solute species in two adjoining immiscible phases. It can for example
be used on interior boundaries separating two liquid phases, a gas-liquid interface, or
on a boundary separating a liquid phase and a solid or porous media.

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

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

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

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 357

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

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

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

https://www.comsol.com/products/specifications/ for more details on
availability.

FURTHER READING
For an example of using a partition condition, see this application example:

Separation Through Dialysis: Application Library path

Chemical_Reaction_Engineering_Module/Mixing_and_Separation/dialysis

Periodic Condition
The Periodic Condition node can be used to define periodicity for the mass transport
between two sets of boundaries. The node prescribes continuity in the concentration
and the mass flux between the “source” and the “destination” side, respectively. Note
that these names are arbitrary and does not influence the direction in which mass is
transported. It is dictated by mass transfer equations in the adjacent domains.

BOUNDARY SELECTION
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.

DESTINATION SELECTION
For more complex geometries, it might be necessary to specify the destination
selection manually. To do so, right-click the Periodic Condition node and choose Manual

358 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Destination Selection. You can then specify the boundaries that constitute the
destination surfaces in the Destination Selection section.

CONSTRAINT SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box. This section contains settings for
specifying the type of constraint and whether to use a pointwise or weak constraint. See
Constraint Settings in the COMSOL Multiphysics Reference Manual for more
information.

ORIENTATION OF SOURCE
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 in the
COMSOL Multiphysics Reference Manual.

ORIENTATION OF DESTINATION
This section appears if the setting for Transform to intermediate map in the Orientation
of Source section is changed from the default value, Automatic, and Advanced Physics
Options is selected in the Show More Options dialog box. For information about the
Orientation of Destination section, see Orientation of Source and Destination in the
COMSOL Multiphysics Reference Manual.

MAPPING BETWEEN SOURCE AND DESTINATION

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
Mapping Between Source and Destination section, see Mapping Between Source and
Destination in the COMSOL Multiphysics Reference Manual.

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

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 359

 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.

SELECTION
The Line Mass Source feature is available for all dimensions, but the applicable selection
differs between the dimensions.

MODEL DIMENSION APPLICABLE GEOMETRICAL ENTITY

2D Points
2D Axisymmetry Points not on the symmetry axis and the symmetry axis
3D Edges

SPECIES SOURCE
·
Enter the source strength, q l,c , for each species (SI unit: mol/(m·s)). A positive value
results in species injection from the line into the computational domain, and a negative
value means that the species is removed from the computational domain.

Line sources located on a boundary affect the adjacent computational domains. This
effect makes the physical strength of a line source located in a symmetry plane twice
the given strength.

FURTHER READING
See the section Mass Sources for Species Transport.

Point Mass Source

The Point Mass Source feature models mass flow originating from an infinitely small
domain around a point.

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

https://www.comsol.com/products/specifications/ for more details on
availability.

360 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

SPECIES SOURCE
·
Enter the source strength, q p,c , for each species (SI unit: mol/s). A positive value
results in species injection from the point into the computational domain, and a
negative value means that the species is removed from the computational domain.

Point sources located on a boundary or on an edge affect the adjacent computational

domains. This has the effect, for example, that the physical strength of a point source
located in a symmetry plane is twice the given strength.

FURTHER READING
See the section Mass Sources for Species Transport.

Open Boundary
Use this node to set up mass transport across boundaries where both convective inflow
and outflow can occur. On the parts of the boundary where fluid flows into the
domain, an exterior species concentration is prescribed. On the remaining parts, where
fluid flows out of the domain, a condition equivalent to the Outflow node is instead
prescribed.

The 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.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 361

 THIN DIFFUSION BARRIER
Specify the Layer thickness, ds, and input a Diffusion coefficient, Ds,c, for each of the
species included.

Thin Impermeable Barrier

This feature models a thin mass transfer barrier. It is available on interior boundaries
and introduces a discontinuity in the concentration across the boundary. On each side,
a no-flux condition is prescribed for the mass transport implying that it acts as a barrier.
The feature can be used to avoid meshing thin structures.

Solving a model involving coupled fluid flow and mass transfer, the Thin Impermeable
Barrier feature can be combined with an Interior Wall feature in order to model a thin
solid wall.

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

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).

362 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Selecting Equilibrium constant defines an equilibrium condition based on the
stoichiometric coefficients, the species activities, and the law of mass action.

For User defined, enter an Equilibrium expression Eeq (dimensionless).

STOICHIOMETRIC COEFFICIENTS
Enter a value for the stoichiometric coefficientνc (dimensionless). The default is 0. Use
negative values for reactants and positive values for products in the modeled reaction.

Species with a stoichiometric coefficient value of 0 are not affected by the Equilibrium
Reaction node.

FURTHER READING
See

• Equilibrium Reaction Theory

• Theory for the Coupling of Mass Transport to Electrochemical Reactions

Surface Reactions
The Surface Reactions node can be used to account for the species boundary flux due
to chemical reactions occurring on a surface (heterogeneous reactions). For a domain
species participating in a surface reaction, the boundary flux corresponds to the
reaction rate at the surface.

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 list.

When defining conditions on boundaries between different phases, see the section
Prescribing Conditions on Fluid-Solid Interfaces.

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

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 363

 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.

When defining conditions on boundaries between different phases, see the section
Prescribing Conditions on Fluid-Solid Interfaces.

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.

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.

When defining conditions on boundaries between different phases, see the section
Prescribing Conditions on Fluid-Solid Interfaces.

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
Porous Electrode Reaction nodes of an Electrochemistry Interface.

The molar source is calculated from the number of electrons, stoichiometric

coefficients, and volumetric current densities of the coupled porous electrode reactions
specified in the Reaction Coefficients subnodes.

364 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

In the Transport of Concentrated Species interface, the molar sources (or sinks) are
multiplied by the species molar masses to obtain the corresponding mass sources.

Additional Reaction Coefficients subnodes are available from the context menu
(right-click the parent node) as well as from the Physics toolbar, Attributes menu.

Note that if you are also modeling the momentum transport and expect a
non-negligible total mass source or sink, which is often the case in gas diffusion
electrodes, you need to also add a corresponding Porous Electrode Coupling node in
the Fluid Flow interface.

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

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.

Current densities from Electrode Reaction (iloc, SI unit: A/m2) or Porous Electrode
Reaction nodes (iv, SI unit: A/m3) of any Electrochemistry interface in the model are
available for selection as the Coupled reaction, and user-defined expressions are also
supported.

Enter the Number of participating electrons nm (dimensionless) and the Stoichiometric

coefficient vc (dimensionless) as explained in the theory section linked below.

Use multiple subnodes to couple to multiple reactions.

Theory for the Coupling of Mass Transport to Electrochemical Reactions

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 365

 Electrode Surface Coupling
Use this node to define a flux boundary condition based on current densities of one or
multiple Electrode Reaction nodes in an Electrochemistry interface.

The flux is proportional to the current densities and the stoichiometric coefficients
according to Faraday’s law as defined by summation over the Reaction Coefficients
subnodes.

Note that if you are also modeling the momentum transport and expect a
nonnegligible total mass flux over the boundary, which is often the case for gas
diffusion electrodes, you need to also add a corresponding Electrode Surface Coupling
node in the Fluid Flow interface.

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

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.

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

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

366 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

MODEL INPUTS
The temperature model input is always available. By default, the Temperature model
input is set to Common model input, and the temperature is controlled from Default
Model Inputs under Global Definitions or by a locally defined Model Input. If a Heat
Transfer interface is included in the component, it controls the temperature Common
model input. Alternatively, the temperature field can be selected from another physics
interface. All physics interfaces have their own tags (Name). For example, if a Heat
Transfer in Fluids interface is included in the component, the Temperature (ht) option
is available for T.

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

CONVECTION
If transport by convection is active, the velocity field of the solvent needs to be
specified. For User defined, enter values or expressions for the velocity components in
the input fields. This input option is always available. You can also select the velocity
field solved for by a Fluid Flow interface added to the model component. These
physics interfaces are available for selection in the Velocity field list.

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

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

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

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

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

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 367

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

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

Note that multiple species, as well as Migration in Electric fields (described below) is
only available for certain COMSOL Multiphysics add-on products. See details: https:/
/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.

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

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

368 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 εp = 1 –  θs, i – θimf, i
i i

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

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

ρb
ε p = 1 – --------
ρ pe

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

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

This subfeature is available when both the Mass transfer in porous media mass transfer
check box and the Convection check box are selected on the Settings window for the
physics interface.

Select the Specify dispersion for each species individually check box to specify the
dispersion tensor DD (SI unit: m2/s) for each species separately. When not selected the
same dispersion tensor DD is used for all species.

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

Select Dispersivity to specify the dispersion in terms of dispersivities (SI unit: m). Select
an option from the Dispersivity model list: Isotropic (the default) or Transverse isotropic
based on the properties of the porous media. For isotropic porous media, specify the
longitudinal and transverse dispersivities. For transverse isotropic porous media,
specify the longitudinal, horizontal transverse, and vertical transverse dispersivities.

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

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

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 369

 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 (described in the COMSOL
Multiphysics Reference Manual), where properties are defined per phase in a similar
manner.

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

account for the corresponding transport mechanism.

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

MODEL INPUTS
The temperature model input is always available. By default, the Temperature model
input is set to Common model input, and the temperature is controlled from Default
Model Inputs under Global Definitions or by a locally defined Model Input. If a Heat
Transfer interface is included in the component, it controls the temperature Common
model input. Alternatively, the temperature field can be selected from another physics
interface. All physics interfaces have their own tags (Name). For example, if a Heat
Transfer in Fluids interface is included in the component, the Temperature (ht) option
is available for T.

370 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

SATURATION
Select Saturation or Liquid volume fraction from the list.

For Saturation, enter a value for s (dimensionless) between 0 and 1. The liquid volume
fraction is then computed from the saturation and porosity as θl = εps.

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

Select a Liquid fraction time change: Liquid fraction constant in time (the default), Time
change in liquid fraction, or Time change in pressure head.

• For Time change in fluid fraction, enter dθ/dt (SI unit: 1/s).
• For Time change in pressure head, enter dHp/dt (SI unit: m/s) and a Specific
moisture capacity Cm (SI unit: 1/m). If a Darcy’s Law interface is included in the
component, the time change in pressure head solved for can be selected.

CONVECTION
If transport by convection is active, the velocity field of the solvent needs to be
specified. For User defined, enter values or expressions for the velocity components in
the input fields. This input option is always available. You can also select the velocity
field solved for by a Fluid Flow interface added to the model component. These
physics interfaces are available for selection in the Velocity field list.

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

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

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

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

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

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 371

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

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

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

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

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

372 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

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

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

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

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

ADSORPTION
Select an Adsorption isotherm — Langmuir, Freundlich, Toth, BET, or User defined to
specify how to compute cP, the amount of species sorbed to the solid phase (moles per
unit dry weight of the solid):

• For Langmuir:

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 373

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

Enter a Langmuir constant kL,c (SI unit: m3/mol) and an Adsorption maximum
cp,max,c (SI unit: mol/kg).

• For Freundlich:

c N ∂c P cP
c P = K F  -------- , K P = -------- = N -----
 c ref ∂c c

Enter a Freundlich constant kF,c (SI unit: mol/kg), a Freundlich exponent NF,c
(dimensionless), and a Reference concentration cref,c (SI unit: mol/m3).
• For Toth:
bT c
c P = c Pmax ----------------------------------------------
N 1 ⁄ NT
( 1 + ( bT c ) T )

and

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

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

and

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

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

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

374 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 cP = f ( c )

For more information, see Adsorption in the theory section.

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

Volatilization
This feature is available when the Mass transfer in porous media check box is selected
on the Settings window for the physics interface.

Use this feature to model mass transfer at the boundary due to volatilization. The
species dissolved in the liquid are assumed to be vaporized at the boundary, and
transported into the surrounding bulk region due to convection and diffusion. The
mass transfer at the boundary is defined as

– n ⋅ J c = – h c ( k G,c c – c Gatm,c )

where hc is the mass transfer coefficient, kG,c the volatilization coefficient, and cGatm,c
the concentration in the surrounding atmosphere.

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

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 | 375

 Species Source
In order to account for consumption or production of species in porous domains, the
Species Source node adds source terms expressions Si to the right-hand side of the
species transport equations.

DOMAIN SELECTION
From the Selection list, choose the domains on which to define rate expression or
expressions that govern the source term in the transport equations.

If there are several types of domains, with subsequent and different reactions occurring
within them, it might be necessary to remove some domains from the selection. These
are then defined in an additional Species Source node.

SPECIES SOURCE
Add a source term Si (SI unit: mol/(m3·s)) for each of the species solved for. Enter a
value or expression in the field of the corresponding species.

Hygroscopic Swelling
The Hygroscopic Swelling multiphysics coupling node ( ) is used for moisture
concentration coupling between the Solid Mechanics interface and either the
Transport of Diluted Species or Transport of Diluted Species in Porous Media
interfaces.

Hygroscopic swelling is an effect of internal strain caused by changes in moisture

content. This volumetric strain can be written as

ε hs = β h M m ( c mo – c mo,ref )

where βh is the coefficient of hygroscopic swelling, Mm is the molar mass, cmo is the
moisture concentration, and cmo,ref is the strain-free reference concentration.

This feature requires a license of either the MEMS Module or the Structural Mechanics
Module. The multiphysics feature will appear automatically if both the Transport of
Diluted Species and the Solid Mechanics interfaces are added to the same component.
For the most current information about licensing, please see See https://
www.comsol.com/products/specifications/.

376 | 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 in the COMSOL Multiphysics Reference Manual.

Out-of-Plane Flux
The out-of-plane flux node is used to prescribe a flux in an out-of-plane domain, and
it can be used to reduce a model geometry to 2D, or even 1D, when the concentration
variation is small in one or more directions. This could be the case for example when
the object to model is thin or slender. Figure 6-1 shows examples of possible situations
in which this type of geometry reduction can be applied.

Jz

Jup

Jdown

Figure 6-1: Geometry reduction from 3D to 1D (top) and from 3D to 2D (bottom).

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

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

∂c i
------- + ∇ ⋅ J i + u ⋅ ∇c i = R i + S
∂t opf, i , (6-1)

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

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 377

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

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

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

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

UPSIDE INWARD FLUX

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

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

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

The available flux type options are General inward flux and External convection. Select
the Species check box for the species for which to specify the flux, and enter a value or
expression for the inward flux in the corresponding field. Use a minus sign when
specifying a flux directed out of the system. To use another boundary condition for a
specific species, click to clear the check box for that species.

Set Flux type to External convection to prescribe a flux to or from an exterior domain
(not modeled) assumed to include convection. The exterior can for example include a
forced convection to control the temperature or to increase the mass transport. In this
case the prescribed mass flux corresponds to

J0 = kc ( cb – c )

where kc is a mass transfer coefficient and cb is the bulk concentration, the typical
concentration far into the surrounding exterior domain.

DOWNSIDE INWARD FLUX

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

378 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

Mass Transfer from a Thin Domain: Application Library path

Chemical_Reaction_Engineering_Module/Tutorials/thin_domain

Fracture
Use this node to model mass transport along thin fractures in porous media. The node
assumes that the transport in the tangential direction along the fracture is dominant as
a result of lower flow resistance.

The Fracture feature has two default subfeatures — the Fluid (Fracture) subfeature
where convection and diffusion are specified and the Fracture Material subfeature
where the porosity εp is defined.

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.

For the Fracture boundary condition, there are a number of Attributes available which
can be accessed either via the Physics Ribbon toolbar (for Windows) or by
right-clicking on the Fracture node. These attributes are identical to the .

Fluid (Fracture)
Use this node to specify the mass transfer in the mobile fluid solvent filling the pores
of a fracture.

It uses the same input options as the Fluid subfeature under the Porous Medium
feature. There are further details about the settings.

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

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 379

 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.

CONVECTION
If transport by convection is active, the velocity field of the solvent needs to be
specified. Select an option from the Velocity field list to specify the convective velocity
along the fracture. For a consistent model, use a Fracture 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

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

The Diffusion settings are similar to those for the diffusion coefficients in
the Fluid node under Porous Medium.

Fracture Material
Specify the Porosity, εp (dimensionless) of the porous matrix. This is by default taken
From material. Select From pellet bed densities to compute the porosity using the (dry
bulk) Bed density ρb and the (single phase) Pellet density ρpe. The porosity is then
defined from

ρb
ε p = 1 – --------
ρ pe

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

380 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

T he T r a ns po r t of D i l u t ed S p ec i es i n
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 the model geometry includes boundaries that should not be included in the mass
transfer simulation, remove those from the selection list.

OUT-OF-PLANE THICKNESS
For 2D components, the Thickness field (default value: 1 m) defines a parameter for the
thickness of the geometry perpendicular to the two-dimensional cross-section. Both
constant and varying thicknesses are supported. The value of this parameter is used,

THE TRANSPORT OF DILUTED SPECIES IN FRACTURES INTERFACE | 381

 among other things, to automatically calculate molar flow rates from the total molar
flux.

TRANSPORT MECHANISMS
Use the Convection check box, available under Additional transport mechanisms, to
control whether to also include convective transport.

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. Its default value is 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.

382 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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 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

THE TRANSPORT OF DILUTED SPECIES IN FRACTURES INTERFACE | 383

 ribbon toolbar (Windows users), Physics context menu (Mac or Linux users), or by
right-clicking to access the context menu (all users).

• Concentration • No Flux
• Flux • Outflow
• Fracture • Reactions
• Inflow • Species Source
• Initial Values

Furthermore, there are the following attributes to the Fracture node

• Adsorption
• Dispersion

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 Boundary material is used as The Transport of Diluted
Species in Fractures Interface is active on boundaries only. The Density ρ of the porous
media is needed when modeling adsorption to the surface of the porous matrix. By
default the option From material is selected.

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). Also activate the check box for the species ci
for which adsorption takes place.

• For Langmuir:

384 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 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

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

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

and

2 2
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 a Saturation concentration cS,c (SI unit: mol/m3).
• For User defined:

THE TRANSPORT OF DILUTED SPECIES IN FRACTURES INTERFACE | 385

 cP = f ( c )

Enter an adsorption isotherm cP,c (SI unit: mol/kg).

For more information, see Adsorption in the theory section.

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

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
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.

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 Fracture.

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

Select the Specify dispersion for each species individually check box to specify the
dispersion tensor DD (SI unit: m2/s) for each species separately. 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.

386 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Select Dispersivity to specify the dispersion in terms of dispersivities (SI unit: m). Select
an option from the Dispersivity model list: Isotropic (the default) or Transverse isotropic
based on the properties of the porous media. For isotropic porous media, specify the
longitudinal and transverse dispersivities. For transverse isotropic porous media,
specify the longitudinal, horizontal transverse, and vertical transverse dispersivities.

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

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

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 fr ( D e ∇c ) = d fr 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
The available options are General inward flux and External convection. If the latter is
chosen, define a Mass transfer coefficient and a Bulk concentration. Specify the flux of
each species individually. To use another boundary condition for a specific species,
make sure that the check box for the mass fraction of that species is unchecked.

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.

THE TRANSPORT OF DILUTED SPECIES IN FRACTURES INTERFACE | 387

 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.

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.

388 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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, included with the Chemical Reaction
Engineering Module, the reaction rate expressions can be automatically generated and
picked up using the drop-down list.

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, εp.

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.

THE TRANSPORT OF DILUTED SPECIES IN FRACTURES INTERFACE | 389

 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.

390 | 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 Inte r f a c 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 | 391

 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:

∂ ρω
( i ) + ∇ ⋅ ( ρω i u ) = – ∇ ⋅ j i + R i (6-2)
∂t

Using the continuity equation, the sum of all species equations, the equation can be
re-cast in its non-conservative form:

∂
ρ (ω i) + ρ ( u ⋅ ∇ )ω i = – ∇ ⋅ j i + R i (6-3)
∂t

This form of the equation is the one used in 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.

OUT-OF-PLANE THICKNESS
For 2D components, the Thickness field (default value: 1 m) defines a parameter for the
thickness of the geometry perpendicular to the two-dimensional cross-section. Both
constant and varying thicknesses are supported. The value of this parameter is used,
among other things, to automatically calculate mass flow rates from the total mass flux.

CROSS-SECTIONAL AREA
For 1D components, enter a Cross-sectional area Ac (SI unit: m2) to define a parameter
for the area of the geometry perpendicular to the 1D component. Both constant and
varying areas are supported.The value of this parameter is used, among other things,
to automatically calculate mass flow rates from the total mass flux. The default is 1 m2.

392 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

TRANSPORT MECHANISMS
The Transport of Concentrated Species interface always accounts for transport due to
convection and 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.
• 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 domain features are enabled:

• Porous Medium
• Porous Electrode Coupling

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 393

 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 = – ρω i  D̃ ik d k – -------- ∇T
T
k=1
˜
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 – ω k ) ∇p – ρω k g k + ω k
p  ρωl gl (6-4)
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 = – --------- ∇φ (6-5)
Mk

where zk is the species charge number, F (SI unit: A·s/mol) is Faraday’s constant and
φ (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.

394 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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 6-40 (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
minimize the impact of any numerical and model introduced errors, use the species
with the highest concentration. By default, the first species is used.

ω1 = 1 –  ωi (6-6)
i=2

CONSISTENT AND INCONSISTENT STABILIZATION

To display this section, click the Show button ( ) and select Stabilization.

• Two consistent stabilization methods are available — 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

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 395

 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
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.

396 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 • 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

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.

The Transport of Concentrated Species in Porous Media Interface

This interface ( ), found under the Chemical Species Transport branch ( ), is used
to calculate the chemical composition in a fluid mixture transported through the
interstices of a porous media. The interface is the same as the Transport of
Concentrated Species interface but it has a Porous Medium node added by default. All
other features for porous media transport is always available.

This interface is dedicated to analyzing mass transport in porous media where the
chemical species may be subjected to convection, diffusion, and migration in an
electric field. The interface also includes reaction rate expressions and source terms for
modeling chemical reactions in porous media. It is also possible to include regions with
free flow.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 397

 The main feature of the interface is the Porous Medium node which adds the governing
equations for the mass fractions of all present species. It has two subnodes, Fluid and
Porous Matrix, which in turn are used to define the physical properties corresponding
to each phase, and to prescribe the transport properties. The latter are typically the
flow field, and when applicable, the electric field. The Porous Medium node supports
the use of a Porous Material (described in the COMSOL Multiphysics Reference
Manual) for defining phase-specific properties, and for sharing them among different
physics interfaces.

When this physics interface is added, the following 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 Concentrated 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 Concentrated Species
Interface.

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.

398 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 For axisymmetric components, COMSOL Multiphysics takes the axial
symmetry boundaries (at r = 0) into account and automatically adds an
Axial Symmetry node to the component that is valid on the axial symmetry
boundaries only.

These nodes are described in this section or as indicated:

• Electrode Surface Coupling • Porous Matrix

• Equilibrium Reaction • Porous Medium
• Fluid • Porous Electrode Coupling1
• Flux • Reaction
• Flux Discontinuity • Reaction Coefficients1
• Inflow • Reaction Sources
• Initial Values • Species Properties
• Mass Fraction • Surface Equilibrium Reaction
• No Flux • Symmetry
• Open Boundary • Thin Impermeable Barrier1
• Out-of-Plane Flux • Transport Properties
• Outflow

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.

Prescribing Conditions on Fluid-Solid Interfaces

Defining conditions on interfaces between different phases, typically a wall in contact
with a fluid, it is worthwhile to be careful with how variables in the conditions are
evaluated. COMSOL Multiphysics supports that variables are defined differently on
adjacent domains (or any other geometry dimension). Evaluating a variable with
differing definitions, the mean value is returned on a boundary separating the different
domains. The density, pressure, or temperature are examples of variables that may
differ in a fluid and a solid. In order to specify on which side a variable is evaluated, the
up and down operators (described in the COMSOL Multiphysics Reference Manual)
can be used.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 399

 Species Properties
Use this node to define parameters specific to each of the species.

The node will change its label depending on what inputs are available in the node. If
only Molar Mass is available, it will be labeled “Species Molar Masses”.

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.

CHARGE
This section is available when the Migration in electric field check box is selected in the
Transport Mechanisms section of the interface. Enter the charge number zw
(dimensionless, but requires a plus or minus sign) for each species.

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 options available in this feature differs between COMSOL products. (See https:/
/www.comsol.com/products/specifications/).

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 6-4 (that is, when a Maxwell–Stefan Diffusion Model is used) and when
calculating the density from the ideal gas law.

400 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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
ρ = -----------
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 ρ.

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

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 401

 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.

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.

402 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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 =  --------
- + ------- 
 DM i Di 
K

For gases, the Kinetic gas theory is often valid and requires the Mean path length λpath
(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.

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.

The temperature (if you are using mobilities based on the Nernst–Einstein relation) is
taken from the Model Inputs section.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 403

 Porous Medium
Use this node to model the composition in a gas or liquid mixture as it is transported
though the interstices of solid porous medium. In addition to transport due to
convection and diffusion, the node contains functionality to include species evolution
through reactions in the fluid phase.

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

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

MODEL INPUTS
Specify the temperature and pressure in the fluid. 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 6-4 (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.

• When present, select a temperature defined by a Heat Transfer interface in the
model. For example, select Temperature (ht) to use the temperature defined by the
Heat Transfer in Fluids interface with the ht name.

404 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Absolute Pressure
Select the source of the Absolute pressure p:

• Select User defined to enter a value or an expression for the absolute pressure.
• When present, select a pressure defined by a Fluid Flow interface present in the
model. For example, select Absolute pressure (spf) to use the pressure defined in a
Laminar Flow interface with spf as the name.

DENSITY
Use this section to define the density of the fluid phase, and to specify 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
ρ = -----------
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 ρ.

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 that solves for the velocity of
the fluid. For example, select Velocity field (spf) to use the velocity field defined by
in a Single-Phase Flow, Laminar Flow interface with spf as the Name.

When the interface is used in a reacting flow multiphysics coupling, the velocity is
automatically defined and the input is disabled.

DIFFUSION
Specify the species molecular and thermal diffusivities in fluid phase in the manner
described for the Transport Properties node.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 405

 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:

εp
f e = ----- (6-7)
τF

For No correction, the effective transport factor is set to one.

–1 ⁄ 3
• For the Millington and Quirk model, the effective transport factor is τ F = ε p .
–1 ⁄ 2
• For the Bruggeman model, the effective transport factor is τ F = εp .
• For the Tortuosity model, specify the tortuosity factor is τF.

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.
• When present, select an electric potential defined by an AC/DC interface that is
present in the model. For example, select Electric potential (ec) to use the electric
field defined 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 and enter one value for each species.

The temperature (if you are using mobilities based or the Nernst–Einstein relation) is
taken from the Model Inputs section.

Porous Matrix
This node defines the porosity, defined as the volume fraction occupied by a fluid
phase, when modeling transport in a Porous Medium.

406 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

εp = 1 –  θs, i – θimf, i
i i

where θs,i and θimf,i are the volume fractions given in Solid and Immobile Fluids
subnodes under the Porous Material node.

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

Electrode Surface Coupling

Use this node to define a flux boundary condition based on current densities of one or
multiple Electrode Reaction nodes in an Electrochemistry interface.

The flux is proportional to the current densities and the stoichiometric coefficients
according to Faraday’s law as defined by summation over the Reaction Coefficients
subnodes. 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.

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

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 407

 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.

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 αED and β 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-ε interface with the Name set to spf.

408 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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 ωi becomes smaller
than its damping limit, ωidl, the rate expression added to species ωi is reduced linearly.
If ωi ≤ 0 for a reactant species, the reaction rate contribution to that species is
completely removed. Similarly, if the mass fraction for a product species ωj becomes
larger than 1 − ωjdl, the rate expression added to that species is damped linearly. If ωj ≥
1 for a product species, the reaction rate contribution to that species is completely
removed.

The default value for the damping limit, ωidl, 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.

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.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 409

 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 εp (εp 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 (ω0,ω1 for example)
• Mole fractions to enter mole fractions (x0,ω1 for example)
• Molar concentrations (SI unit: mol/m3) to enter molar concentrations (c0,ω1 for
example)
• Number densities (SI unit: 1/m3) to enter number densities (n0,ω1 for example)
• Densities (SI unit: kg/m3) to enter densities (ρ0,ω1 for example)

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

410 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 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 ρm0.

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: ωi = ωi,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.

When defining conditions on boundaries between different phases, see the section
Prescribing Conditions on Fluid-Solid Interfaces.

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.

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 (6-8)

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 411

 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 ωi, the temperature, the pressure or even the electric
potential.

When defining conditions on boundaries between different phases, see the section
Prescribing Conditions on Fluid-Solid Interfaces.

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 + ρuω 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 non-negligible 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.

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

412 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 j 0, i = k ω, i ( ω b, i – ω i ) (6-9)

where kω,i is a mass transfer coefficient and ωb,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: ωi = ω0,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: ρi = ρ0,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 (ω0,ω1, for example)
• Mole fractions to enter mole fractions (x0,ω1 for example)
• Molar concentrations (SI unit: mol/m3) to enter molar concentrations (c0,ω1, for
example)
• Number densities (SI unit: 1/m3) to enter number densities (n0,ω1, for example)
• Densities (SI unit: kg/m3) to enter densities (ρ0,ω1, for example)
• Mass flow rates (SI unit: kg/s) to enter the total mass flow over the boundary
(Jin,ω1, for example)

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.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 413

 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.

Out-of-Plane Flux
The out-of-plane flux node is used to prescribe a flux in an out-of-plane domain, and
it can be used to reduce a model geometry to 2D, or even 1D, when the variation of
mass fraction is small in one or more directions. This could be the case for example
when the object to model is thin or slender. Figure 6-1shows examples of possible
situations in which this type of geometry reduction can be applied.

jz

jup

jdown

Figure 6-2: Geometry reduction from 3D to 1D (top) and from 3D to 2D (bottom).

For a 1D component this node adds a single out-of-plane mass flux j0,z,i for species i.
For a 2D component two fluxes can be prescribed for each species; j0,u,i for the upside
of the domain, and j0,d,i for the downside of the domain.

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

414 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 ∂
ρ (ω i) + ρ ( u ⋅ ∇ )ω i + ∇ ⋅ j i = R i + S opf, i , (6-10)
∂t

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

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

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

j 0, i = k w, u, i ( w b, u, i – w i ) + k w, d, i ( w b, d, i – w i )

where kω,i is a mass transfer coefficient and ωb,i is the bulk mass fraction, the typical
mass fraction far into the surrounding exterior domain. The prescribed flux, j0, can
include any arbitrary user-specified expressions. It can be a constant or a function of a
dependent variable or independent variables.

UPSIDE INWARD FLUX

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

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

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

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

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 ω, i ( ω b, i – ω i )

where kω,i is a mass transfer coefficient and ωb,i is the bulk mass fraction, the typical
mass fraction far into the surrounding exterior domain.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 415

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

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

Mass Transfer from a Thin Domain: Application Library path

Chemical_Reaction_Engineering_Module/Tutorials/thin_domain

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 ⋅ ρD i ∇ω i = 0

• For the Fick’s Law Diffusion Model:

f
– n ⋅ ρD i ∇ω 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 ⋅ ( ρω i u + j i ) = 0

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.

416 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Flux Discontinuity
The Flux Discontinuity node represents a discontinuity in the mass flux across an interior
boundary:

–n ⋅ ( Nd – Nu ) = N0 N = ( ρω 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 (ω0,ω1, for example)
• Mole fractions to enter mole fractions (x0,ω1, for example)
• Molar concentrations (SI unit: mol/m3) to enter molar concentrations (c0,ω1, for
example)

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 417

 • Number densities (SI unit: 1/m3) to enter number densities (n0,ω1, for example)
and to describe the number of particles per volume n = n0
• Densities (SI unit: kg/m3) to enter densities (ρ0,ω1, 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

ν
∏ ai i
i ∈ products
K eq = ----------------------------------
–ν
∏ ai i
i ∈ reactants

where νi 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.

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

418 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

STOICHIOMETRIC COEFFICIENTS
Enter a value for the stoichiometric coefficientν 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.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 419

 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

420 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

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

MIXTURE PROPERTIES

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

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

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

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

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

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

THE CHEMISTRY INTERFACE | 421

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

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

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

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

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

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

422 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Surface Species
The Surface Species table is available when there is at least one surface species (with
“(ads)” as suffix).

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

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

Solid Species
The Solid Species table is available when there is at least one solid species (with “(s)” as
suffix).

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

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

Aqueous Species
The Aqueous Species table is available when there is at least one aqueous species (with
“(aq)” as suffix).

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

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

Equilibrium Reaction Rate Table

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

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

CALCULATE TRANSPORT PROPERTIES

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

THE CHEMISTRY INTERFACE | 423

 built-in Automatic expressions fit 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
This section is available when the Thermodynamics check box is cleared.

Select the Use activity check box to solve for species activities instead of species
concentrations, which is a common approach when non-ideal fluids are modeled.

An activity coefficient other than 1 can be set for each species for the Species node in
the Species Concentration/Activity section.

CHEMKIN IMPORT FOR SPECIES PROPERTIES

It is available when the Thermodynamics check box is cleared.

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

gas phase.

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

424 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Feature Nodes Available for the Chemistry Interface
The following feature nodes are available from the Chemistry ribbon toolbar (Windows
users), Chemistry context menu (Mac or Linux users), or right-click to access the
context menu (all users).

• Equilibrium Reaction Group • Species

• Reaction • Species Activity
• Reaction Thermodynamics1 • Species Group
• 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 equation in the Formula field. The chemical equation should be of the
format “A + B arrow C + D”. Here, A and B are reactants, C and D are product species,
and arrow denotes a reaction arrow. The participating species should be written with
Valid Species Names. Valid reaction arrows are “<=>” for reversible reaction, “=>” for
irreversible reaction, and “=” for equilibrium reaction. Species can be given trivial
names, or their chemical formulas can be used as names. Examples of valid formulas
are; “carbon+oxygen=>carbondioxide”, and “C(s)+O2(g)=>CO2(g)”.

Click Apply to make the interface examine the species taking part in the chemical
equation, and automatically add the associated Species features to the Model Builder.

Balance ( )
Use the Balance button to automatically calculate the stoichiometric coefficients such
that the number of atoms of each kind are the same on both sides of the reaction. This
turns, for example, the formula “H2+O2=>H2O” into “2H2+O2=>2H2O”. The
balancing involves parsing all participating species for elements in the periodic table. It

THE CHEMISTRY INTERFACE | 425

 therefore requires that all species in the Formula field are written either using their
chemical formula, say “H2O”, or that each species in the reaction have an enabled
Chemical Formula field in their Species node. For example, it is possible to balance the
formula “H2+O2=>water” as long as there is a Species node with the name “water”
already present, and an enabled Chemical Formula.

For automatic reaction balancing to be successful, requires that the problem is well
posed. One example of a problem that is not well posed is “C+H2=>CH4+C2H6”, in
which case any ratio of CH4/C2H6 could be obtained. Another example is
“H2=>O2” where not all elements are present on both sides.

Reaction Type
Select the Reaction type — Reversible, Irreversible, or Equilibrium — or edit the
expression directly in the Formula field. In the latter case, specify the reaction type with
a delimiter separating the two sides of the equation:

• <=> denotes a Reversible reaction

• => denotes an Irreversible reaction
• = denotes a reaction at chemical Equilibrium

Each Reaction type has its own set of reaction kinetics:

• If the reaction is Reversible or Irreversible, the reaction rate for reaction i contributes
to the change in species i as follows:

Ri =  νij rj (6-11)
j

where νij is the stoichiometric coefficient.

• If it is an Equilibrium reaction, the equilibrium expression is equal to the equilibrium

constant:
K eq = K eq0

REACTION RATE
This section is available when the Reaction type is either Reversible or Irreversible.

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

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

426 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 – ν ij
∏
f
rj = kj ci (6-12)
i ∈ react

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

– ν ij ν
∏ ∏
f r
rj = kj ci – kj c i ij (6-13)
i ∈ react i ∈ prod

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

Arbitrary Rate Expression

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

Consider for example the reaction:

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

THE CHEMISTRY INTERFACE | 427

 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 6-3: The reaction order can be manually specified for a user defined reaction rate.

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 6-12).

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

428 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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)

EQUILIBRIUM SETTINGS
This section is available for equilibrium reactions, and for reversible reactions when the
Specify equilibrium constant check box has been selected.

Equilibrium Expression
For an equilibrium reaction, specify the Equilibrium expression. When the Equilibrium
expression is set to Automatic the following expression is used:

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

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

THE CHEMISTRY INTERFACE | 429

 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.

Enthalpy of Reaction
The Enthalpy of reaction H (SI unit: J/mol) is calculated by the interface from species
properties and the related stoichiometric coefficients:

Hj =  ν ij h i –  ( – ν ij )h i (6-14)
i ∈ prod i ∈ react

Entropy of Reaction
The Entropy of reaction S (SI unit: J/(mol·K)) comes from a similar expression:

Sj =  ν ij s i –  ( – ν ij )s i (6-15)
i ∈ prod i ∈ react

In Equation 6-14 and Equation 6-15, hi and si are the species’ molar enthalpy and
molar entropy, respectively.

430 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Enter these quantities in the Species Thermodynamic Expressions section for the Species
node either by using the predefined polynomial or by providing a custom expression
or constants.

The stoichiometric coefficients, νij, are defined as being negative for reactants and
positive for products. Using Equation 6-14 and Equation 6-15 to equate the Gibbs
free energy of reaction enables the equilibrium constant to be expressed according to
Equation 6-14.

Heat Source of Reaction

The Heat source of reaction (SI unit: W/m3) is automatically computed from the heat
of each reaction j, given by:

Qj = –Hj rj

Using the Reaction Node

Species
When a Reaction is defined, a Species node ( ) is automatically generated for the
participating reactants and products. This feature enables you to review and enter
species specific information regarding chemical kinetics, thermodynamics and
transport properties.

It is also possible to add and define an individual Species node: on the Chemistry toolbar
click Species or right-click the Chemistry node and select it from the context menu.

NAME
When a Species node is automatically generated using the Formula text field for the
Reaction node, the Name is also automatically generated.

For a Species node added individually, enter a Name in the field and click Apply. By
entering a name consisting of elements from the periodic table, the molar mass is
calculated and added in the Chemical Formula section. The species charge, and type, are
also deduced from the species name.

Valid Species Names

THE CHEMISTRY INTERFACE | 431

 TYPE
Select a species type — Bulk species, Surface species, or Solvent. The latter is only
available when a diluted solution is assumed. That is when Type is set to Diluted Species
in the Mixture Properties section (in the interface level).

Bulk species and Solvent are solved for volumetric concentrations (SI unit: mol/m3),
while Surface species are solved for surface concentration (SI unit: mol/m2). The
compositions for Bulk species and Solvent use the syntax c_speciesname, while Surface
species uses csurf_speciesname_surf.

When Surface species is selected, the corresponding reaction formula introduces (ads)
after the species notation and changes the species’ name to speciesname_surf.
Additionally, the Species node name is updated in a similar fashion.

CHEMICAL FORMULA
The Chemical Formula section contains the species chemical formula, Molar mass, M,
and Charge, z.

If the name entered for the species consists of only elements from the periodic table,
and optionally charge and phase indication, then the Chemical Formula field will be
populated with the name entered in the Name section, and the molar mass and charge
will be added to this section. The species molar mass is computed from the mass of
occurring individual elements1. The rules for writing chemical formulas are the same
as those for Species names.

Valid Species Names

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. By entering a
chemical formula consisting only of elements from the periodic table (and optionally
charge and phase indication), the molar mass, and charge are derived automatically.

When needed, the Molar mass can be edited in the corresponding text field. Editing
the Chemical formula and pressing apply will override the molar mass and charge
fields.The Charge field cannot be edited as long as a chemical formula is enabled.

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.

432 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

With an enabled Chemical Formula it is possible to use the trivial name of a species and
balance reactions. Having added the Species water, oxygen, and hydrogen, and filled
in H2O, O, and H in their respective chemical formula sections, the Formula
oxygen+hydrogen=water is balanced into oxygen+2hydrogen=water by clicking
Balance in the Reaction node.

It is possible to specify the species density ρ when the fluid Mixture is specified as Liquid.
The default value is that of water at 293 K.

REACTION RATE
Change the Automatic default setting to User defined to use a species reaction rate other
than the one set up in the associated Reaction node. For individual species, use the User
defined option to set a reaction rate other than zero (that is, nonreactive).

Edit either the Rate expression (SI unit: mol/(m3·s)), the Surface rate expression (SI
unit: mol/(m2·s)), or both. For a bulk species, both expressions appear if surface
reactions are present since the reaction of the species can depend both on bulk reaction
R and surface reaction Rads rates. For a surface species, only the surface reaction rate
Rads appears.

ADDITIONAL SOURCE
The Additional Source section is available in order to include additional rate
contribution for the species to the reaction kinetics. When the Additional source check
box is selected, add an Additional rate expression in the text field (SI unit: mol/m3).

CONSTANT CONCENTRATION/ACTIVITY
To account for non-ideality in the fluid mixture, adjust the activity coefficient in the
Activity coefficient input field. This input field is only shown if activity instead of
concentration has been chosen in the interface, that is, the Use activity check box is
selected on the Chemistry interface Settings window

Click to select the Keep concentration/activity constant check box if the species
concentration or activity should be treated as constant.

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.

THE CHEMISTRY INTERFACE | 433

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

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.

434 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

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

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

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

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

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

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

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

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

THE CHEMISTRY INTERFACE | 435

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

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

Δr H
E therm = – ----------- (6-16)
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.

436 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

For the case when reaction kinetics data are entered manually into the Reaction table
and temperature dependent reaction kinetics apply, right-click to add a Reaction
Thermodynamics subnode or select it from the Chemistry toolbar, Attributes menu. In
it, the Enthalpy of Reaction (J/mol) for each reaction can be specified.

REACTION TABLE
The reversible reactions in the Reaction table are numbered and contain reactants,
products, and kinetic parameters describing the reaction. Use the buttons under the
Reaction table to add and sort the reaction details.

• In general, use the Move Up ( ), Move Down ( ), and Delete ( ) buttons and
the fields under tables to edit the table contents. Or right-click a table cell and select
Move Up, Move Down, or Delete.
• The Add button ( ) adds default reactant, A, and product, B, with a default. Click
the corresponding field to edit the reactant, product, or parameters. After editing
the Species Group node is also updated. It is created together with the reaction
group.
• You can save the parameters to a text file to reuse in other models. Click the Save to
File button ( ) and enter a File name in the Save to File dialog box, including the
extension .txt. Click Save to store the parameters in a text file or in a Microsoft
Excel Workbook spreadsheet if the license includes LiveLink™ for Excel®. The
information is saved in space-separated columns in the same order as displayed on
screen. When saving to Excel, an Excel Save dialog box appears where you can specify
the sheet and range and whether to overwrite existing data or include a header.
• You can import or load data in files from a spreadsheet program, for example, with
the Load from File button ( ) and the Load from File dialog box that appears. Data
must be separated by spaces or tabs. If there is already data in the table, imported
parameters are added after the last row. Move or edit rows as needed. If the license
includes LiveLink™ for Excel® you can also load parameters from a Microsoft Excel
Workbook spreadsheet. Then an Excel Load dialog box appears where you can specify
the sheet and range and whether to overwrite existing data. It is also possible to
import from a spreadsheet containing a separate column for units.

CREATE REACTION AND SPECIES

Enter a reaction number in the Moving reaction (with the number) from table text field
and click Create Reaction to remove the reaction from the Reaction table to the model
tree. This introduces a reaction node named after the reaction number and species
names and simultaneously creates corresponding species nodes. This action is

THE CHEMISTRY INTERFACE | 437

 powerful, since it enables all the editing possibilities available for Reaction and Species
nodes.

Equilibrium Reaction Group

The Equilibrium Reaction Group node ( ) allows for input of a large number of
equilibrium reactions in the same table. This node functions in the same way as the
Reversible Reaction Group for reversible reactions.

Add the node from the Chemistry toolbar or right-click Chemistry and add it from the
context menu.

For the case when reaction kinetics data are entered manually into the Reaction table
and temperature dependent reaction kinetics apply, right-click to add a Reaction
Thermodynamics subnode or select it from the Chemistry toolbar, Attributes menu. In
it, the Enthalpy of Reaction (J/mol) for each reaction can be specified.

REACTION TABLE
The equilibrium reactions in the table are numbered and contain reactants, products,
and kinetic parameters describing the reaction. Use the buttons under the Reaction
table to add and sort the reaction details.

• In general, use the Move Up ( ), Move Down ( ), and Delete ( ) buttons and
the fields under tables to edit the table contents. Or right-click a table cell and select
Move Up, Move Down, or Delete.
• The Add button ( ) adds default reactant, A, and product, B, with a default. Click
the corresponding field to edit the reactant, product, or parameters. After editing
the Species Group node is also updated. It is created together with the reaction
group.
• You can save the parameters to a text file to reuse in other models. Click the Save to
File button ( ) and enter a File name in the Save to File dialog box, including the
extension .txt. Click Save to store the parameters in a text file or in a Microsoft
Excel Workbook spreadsheet if the license includes LiveLink™ for Excel®. The
information is saved in space-separated columns in the same order as displayed on
screen. When saving to Excel, an Excel Save dialog box appears where you can specify
the sheet and range and whether to overwrite existing data or include a header.
• You can import or load data in files from a spreadsheet program, for example, with
the Load from File button ( ) and the Load from File dialog box that appears. Data
must be separated by spaces or tabs. If there is already data in the table, imported

438 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 parameters are added after the last row. Move or edit rows as needed. If the license
includes LiveLink™ for Excel® you can also load parameters from a Microsoft Excel
Workbook spreadsheet. Then an Excel Load dialog box appears where you can specify
the sheet and range and whether to overwrite existing data. It is also possible to
import from a spreadsheet containing a separate column for units.

Species Group
The Species Group node ( ) contains information on a molecular level about the
volumetric species and the surface species present in the model. The Property for
Volumetric Species or Property for Surface Species tables typically collect parameters from
when importing CHEMKIN transport files.

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

For the case of temperature dependent reaction kinetics, a Species Thermodynamics

subnode is automatically created in which the thermodynamic properties of the species
can be specified.

Reaction Thermodynamics
The Reaction Thermodynamics subnode ( ), the Enthalpy of Reaction (J/mol) of
each reaction can be specified. This node overrides all the automatically calculated
reaction enthalpies as defined in the Species Thermodynamics subnode.

Add the Reaction Thermodynamics node from the Chemistry toolbar, Attributes menu.
Alternatively, right-click a Reversible Reaction Group or Equilibrium Reaction Group
to add the Reaction Thermodynamics subnode.

Species Activity
The Species Activity node ( ) creates variables for the activities of all the species/
surface species present in the Species Group parent feature. Edit the Activity coefficient
field in the Species Activity or Surface Species Activity tables by clicking in these.

Species Activity is a subnode to the Species Group node. It is automatically generated

when nonideality in the fluid mixture is accounted for; when the Use activity check box
is selected in the Activity section.

THE CHEMISTRY INTERFACE | 439

 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.

440 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

The Nernst–Planck–Poisson
Equations Interface
The Nernst-Planck-Poisson Equations interface ( ), found under the Chemical Species
Transport branch ( ) when adding a physics interface, is a predefined multiphysics
interface for modeling transport of electrolyte species without the otherwise common
assumption of local electroneutrality. This allows for simulating charge separation that
typically arises close to an electrode surface, where ions in the electrolyte are attracted
and repelled by unscreened excess charge on the electrode. The charge separation
region, also called the diffuse double layer, normally extends a few nanometers away
from the electrode surface into the electrolyte. The study of the charge separation is
important to applications that consider very thin layers of electrolyte, such as
electrochemical capacitors, atmospheric corrosion problems, ion-selective field effect
transistors (ISFETs), and nanoelectrochemistry.

The Nernst–Planck–Poisson Equations predefined multiphysics interface adds The

Transport of Diluted Species Interface ( ) (with Migration enabled), which solves
for the Nernst–Planck equations without charge neutrality, and The Electrostatics
Interface( ), that solves for the Poisson’s equation.

A Space Charge Density Coupling ( ) multiphysics node is also added. This node
computes the local space charge, based on the local concentrations and species charges
in the Transport of Diluted Species interface, and adds it to Poisson’s Equation in the
Electrostatics interface.

THE NERNST–PLANCK–POISSON EQUATIONS INTERFACE | 441

 Finally, a Potential Coupling ( ) multiphysics node is added that applies the
potential dependent variable in the Electrostatics interface into the migration term of
the Transport of Diluted Species interface.

• The Multiphysics Branch in the COMSOL Multiphysics

Reference Manual.
• The Transport of Diluted Species Interface
• The Electrostatics Interface
• Space Charge Density Coupling
• Potential Coupling

Diffuse Double Layer: Application Library path

Battery_Design_Module/General_Electrochemistry/
diffuse_double_layer

442 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

The Electrophoretic Transport
Interface
The Electrophoretic Transport (el) interface ( ), found under the Chemical Species
Transport branch ( ), is used to solve for the electrophoretic transport of an
arbitrarily number of species in water-based system, subject to potential gradients. The
species transported can be any combination of weak and strong acids and bases,
ampholytes, and uncharged species. The transport of masses and charge is based on the
Nernst–Planck equations for molecular transport, in combination with
electroneutrality, dissociation equilibria for weak acids, bases and ampholytes as well as
the water auto-ionization reaction.

The physics interface can simulate most forms of electrophoresis modes, such as zone
electrophoresis, isotachophoresis, isoelectric focusing, and moving boundary
electrophoresis.

Gel electrophoresis can be simulated by the inclusion of immobile charged species.

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

The dependent variables are the electrolyte potential, and the molar concentrations of
the included species, added individual by each species node in the model tree.

SETTINGS
The Label is the default physics interface name.

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

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

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

THE ELECTROPHORETIC TRANSPORT INTERFACE | 443

 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

444 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 neglected. This setting is usually accurate enough and is computationally faster. If
required, select Full residual instead.

INCONSISTENT STABILIZATION
To display this section, click the Show More Options button ( ) and select Stabilization
in the Show More Options dialog box. By default, the Isotropic diffusion check box is not
selected, because this type of stabilization adds artificial diffusion and affects the
accuracy of the original problem. However, this option can be used to get a good initial
guess for under-resolved problems.

ADVANCED SETTINGS
To display this section, click the Show More Options button ( ) and select Advanced
Physics Options in the Show More Options dialog box. Normally these settings do not
need to be changed. Select a Convective term — Nonconservative form (the default) or
Conservative form. The conservative formulation should be used for compressible flow.

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

The concentration variables are set to use Linear elements by default.

The potential variable is set to use Quadratic elements by default.

The Compute boundary fluxes check box is activated by default so that COMSOL
Multiphysics computes predefined accurate boundary flux variables. When this option
is checked, the solver computes variables storing accurate boundary fluxes from each
boundary into the adjacent domain.

If the check box is cleared, the COMSOL Multiphysics software instead computes the
flux variables from the dependent variables using extrapolation, which is less accurate
in postprocessing results but does not create extra dependent variables on the
boundaries for the fluxes.

The flux variables affected in the interface are:

• <name>.nIl, where <name> is the name of the interface (default is el), set on the
interface top node. This is the normal electrolyte current density.
• <name>.ntflux_<species_name> is the Species name (see Common Settings for
the Species Nodes in the Electrophoretic Transport Interface below). This is the
normal total flux for each species.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 445

 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

446 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Each species node add a dependent variable for the concentration. The initial and
boundary condition, as well as adding additional source reaction terms, for each
species concentration is controlled by adding subnodes to the species nodes:

• Concentration
• Flux
• Inflow
• Initial Concentration
• No Flux
• Outflow
• Species Source

The Ampholyte, Weak Acid, and Weak Base nodes are dissociation species and may
define an arbitrary number of dissociation steps. Each dissociation step is defined by
its pKa (the acid equilibrium constant) parameter. For the weak bases the pKa refers
to the acid constant of the conjugate acid. Each dissociation step adds one additional
subspecies concentration variable so that the concentration dependent variable
represents the sum of all subspecies, and initial and boundary conditions are defined
with respect to this total concentration.

All species node have a setting for the Species name, which needs to be unique. The
species name is used for naming of all related variables of the species. For species nodes
not defining any subspecies, the concentration variables are named as
<name>.c_<species_name> where <name> is the name of the interface (default is el),
set on the interface top node, and <species_name> is the Species name. For
dissociation species nodes defining multiple subspecies, the concentration nodes are
named as <name>.c<X>_<species_name> where <X> is the integer from 1 up to the
total number of subspecies. Note that the Solvent node automatically defines the
concentration variables for protons (<name>.cH) and hydroxide ions (<name>.cOH).

All species except the Uncharged Species carry charge and contribute to the total
electrolyte current which is used in the equation for solving the electrolyte potential.

The Immobile Species check box can be used to lock the concentration of a species, to,
for instance, define the immobile charges in a ion-selective membrane or a gel. When
the check box is enabled the concentration of the species is not added as a dependent
variable to the model; instead the concentration will be set to the value provided in the
Concentration field. The contribution to the electrolyte current for immobile species is
zero.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 447

 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
Linderstrøm-Lang assumption. The latter is usually used for macromolecules.

448 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

To add a node, go to the Physics toolbar, no matter what operating system

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

• Ampholyte • No Flux
• Concentration • Outflow
• Current • Porous Matrix Properties
• Current Density • Potential
• Current Source • Protein
• Flux • Species Source
• Fully Dissociated Species • Solvent
• Inflow • Uncharged Species
• Initial Concentration • Weak Acid
• Initial Potential • Weak Base
• Insulation

For axisymmetric components, COMSOL Multiphysics takes the axial

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

In the COMSOL Multiphysics Reference Manual, see Table 2-4 for links
to common sections and Table 2-5 for common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 449

 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.

450 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

See also Common Settings for the Species Nodes in the Electrophoretic Transport
Interface and Diffusion and Migration Settings.

Weak Acid
The Weak acid node supports multiple dissociation steps, where the acid of the first
dissociation step is uncharged.

The species may be either Monoprotic, subject to one dissociation step only, or
Polyprotic. For the latter case any Number of dissociation steps larger than one may be
used.

See also Common Settings for the Species Nodes in the Electrophoretic Transport
Interface and Diffusion and Migration Settings.

Weak Base
The Weak base node supports multiple dissociation steps, where the base of the last
dissociation step is uncharged.

The species may be either Monoprotic, subject to one dissociation step only, or
Polyprotic. For the latter case any Number of dissociation steps larger than one may be
used.

Note that the pKa refers to the acid constant of the conjugate acid of the weak base.

See also Common Settings for the Species Nodes in the Electrophoretic Transport
Interface and Diffusion and Migration Settings.

Ampholyte
Use the Ampholyte node generically to define any species where the average charge
depends on the pH of the solution. The Dissociation model may be based either on a
set of Equilibrium constants or an Average charge.

When using the Equilibrium constants the Base charge in last dissociation step, Z0
(unitless), needs to be set.

The Average charge, Z (unitless) parameter is typically a function of pH and may be

added as an analytical function or an interpolation polynomial under Definitions. The
average squared charge, used in the electrolyte potential equation, is calculated
automatically based on Z .

THE ELECTROPHORETIC TRANSPORT INTERFACE | 451

 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.

452 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

This node is typically used to model electrode surfaces where the electrode kinetics
depends on the electrolyte potential.

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

Insulation
The Insulation boundary condition describes the walls of a cell or the boundaries of the
cell that do not face an electrode (or a reservoir containing an electrode). The
boundary condition imposes the following equation:

il ⋅ n = 0

Potential
Add the Potential node on a boundary to set a fixed potential. This node is typically
used to model electrode surfaces or boundaries facing an electrolyte reservoir.

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

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

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

This node may be added as a subnode to any species node. See also Common Settings
for the Species Nodes in the Electrophoretic Transport Interface.

In order to account for consumption or production of species, for example in porous

electrodes or as a result of reversible reactions, the Species Source node adds source
terms expressions S (SI unit: mol/(m3·s) to the right-hand side of the transport
equation of the parent species.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 453

 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.

454 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

INWARD FLUX
Enter a value or expression for the species mass flux J0. Use a minus sign when
specifying a flux directed out of the system.

External convection
Set Flux type to External convection to prescribe a flux to or from an exterior domain
(not modeled) assumed to include convection. The exterior can for example include a
forced convection to control the temperature or to increase the mass transport. In this
case the prescribed mass flux corresponds to

J0 = kc ( cb – c )

where kc is a mass transfer coefficient and cb is the bulk concentration, the typical
concentration far into the surrounding exterior domain.

Inflow
This node is available when you select the Convection check box on the physics interface
Settings window.

Use this node to specify the species concentrations at an inlet boundary.

BOUNDARY CONDITION TYPE

The option Concentration constraint constrains the concentration values on the
boundary by the use of pointwise constraints. When using this option the boundary
condition is identical to the Concentration node.

The other option, Flux (Danckwerts) can be more stable and fast to solve when high
reaction rates are anticipated in the vicinity of the inlet. Oscillations on the solutions
can also be avoided in such cases. The latter condition uses a flux boundary condition
based on the velocity across the boundary and the concentration values.

Outflow
Set this condition at outlets where species are transported out of the model domain by
migration or fluid motion. It is assumed that migration and convection are the
dominating transport mechanisms across outflow boundaries, and therefore that
diffusive transport can be ignored; that is:

n ⋅ ( – D ∇c ) = 0

THE ELECTROPHORETIC TRANSPORT INTERFACE | 455

 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.

456 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Enter the Number of bulk species. Use the Add bulk concentration ( ) and Remove bulk
concentration ( ) buttons as needed. The same number of Bulk concentrations cb,
cb2, cb3, … are then listed in the table.

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

CONSISTENT AND INCONSISTENT STABILIZATION

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

By default the Compensate for boundary stretching check box is selected for the Surface
Properties node. This section is then used to stabilize the tangential mesh velocity
term.

When the Compensate for boundary stretching check box is cleared (not selected), and
for fixed geometries or moving geometries, the stabilization has no effect.

See Surface Reaction Equations on Deforming Geometries for more information.

• Boundary, Edge, Point, and Pair Nodes for the Surface Reactions
Interface
• Theory for the Surface Reactions Interface

Soluble Lead–Acid Redox Flow Battery: Application Library path

Battery_Design_Module/Flow_Batteries/pb_flow_battery

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),

THE SURFACE REACTIONS INTERFACE | 457

 Physics context menu (Mac or Linux users), or right-click to access the context menu
(all users).

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

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

These nodes are described in this section:

• Initial Values
• Reactions
• Surface Concentration
• Surface Properties

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

In the COMSOL Multiphysics Reference Manual see Table 2-4 for links
to common sections and Table 2-5 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Surface Properties
Use the Surface Properties node to define the density of sites, the site occupancy
number, and the surface diffusion.

SPECIES CONSERVATION ON DEFORMING GEOMETRY

The Compensate for boundary stretching check box is selected by default. Click to clear
the check box if required.

SITES
Enter a value or expression for the Density of sites Γs (SI unit: mol/m2). The default
is 2 x 10-5 mol/m2.

Enter a Site occupancy number σi (dimensionless), indicating how many surface sites a
surface species block upon adsorption.

This section is only present if the number of surface species is 1 or higher.

458 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

SURFACE DIFFUSION
Select a Surface material from the list. The default is None.

For each surface concentration species, the default Diffusion coefficient Di (SI unit: m2/
s) is User defined. Select Isotropic, Diagonal, Symmetric, or Full depending on the
characteristics of the surface, and then enter values or expressions in the field or matrix.

This section is only present if the number of surface species is 1 or higher.

BULK SPECIES
For each bulk species enter the Molar mass Mi (SI unit: kg/mol) and the Density ρi
(SI unit: kg/m3). The default molar mass is 0.144 kg/mol and the default density is
5320 kg/m3).

This section is only present if the number of bulk species is 1 or higher.

Surface Reaction Equations on Deforming Geometries

Initial Values
The Initial Values node allows the initial value or guess for the surface and bulk
concentrations.

INITIAL VALUES
Based on the number of surface species and number of bulk species entered for the
physics interface under Dependent Variables section, enter values for the same number
of Surface concentration cs, cs2, cs3, … (SI unit: mol/m2) and Bulk concentration cb,
2
cb2, cb3, … (SI unit: mol/m ) in each field.

Reactions
The Reactions node adds rate expression terms to the species transport equations in
order to account for consumption or production of species due to reactions.

REACTION RATE FOR SURFACE SPECIES

Add a reaction rate expression, Rs,cs1,cs2… (SI unit: mol/(m2·s)), for each surface
species taking part in a surface reaction.

This section is only present if the number of surface species is 1 or higher.

THE SURFACE REACTIONS INTERFACE | 459

 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.

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.

460 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

The Reacting Flow Interfaces
The Battery Design 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 Porous
Medium feature can be added in order to model flow in porous media by solving the
Brinkman equations.

THE REACTING FLOW INTERFACES | 461

 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. When a Heat Transfer and a Chemistry interface are selected, use
this coupling to simulate heat transfer additionally to mass transport and reactions.

The coupling adds the heat source of reaction when a heat transfer interface is selected.
No additional heat source needs to be defined to account for it in the heat transfer
interface. It also accounts for the multiphysics stabilization terms, for work due to
pressure forces and viscous dissipation.

Select a Fluid Flow interface and a Species transport interface to couple fluid flow with
mass transport. Chemistry and Heat Transfer are optional. They can be set to None when
the coupling is used to simulate isothermal mixtures.

When a Chemistry interface is selected and Heat Transfer is set to None, fluid properties
are taken from the Chemistry interface. Set the Temperature to evaluate the fluid
properties synchronized with all the physics interfaces at the given temperature.

Select a Chemistry interface and Heat Transfer interface in order to account for the heat
of reaction, enthalpy diffusion, viscous heating and mass fluxes contributing to the
heat and energy balance.

When Chemistry is set to None and a Heat Transfer interface is selected, the
coupling is solved in the same way as when no Heat Transfer interface is
selected. Thermodynamic properties are required by the Heat Transfer
interface.

462 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 The pressure, velocity, and temperature variables of the Reacting Flow
coupling node are set to the Common Model Input values of the Default
Model Inputs node on the complementary selection, that is, all domains
except those from the Selection list. It allows to couple multiple fluid flow
or transport of species interfaces with a single heat transfer interface. See
Default Model Inputs in the COMSOL Multiphysics Reference Manual
for details.

DOMAIN LEVEL SYNCHRONIZATION

The Reacting Flow coupling synchronizes the features from a Chemistry interface, Heat
Transfer interface, Single-Phase Flow, or Brinkman Equations, interface and a
Transport of Concentrated Species interface. When the Chemistry interface is not
selected, the density in the Single-Phase Flow interface is automatically synchronized
to the one defined by the Transport of Concentrated Species interface.

The velocity field used by the Transport of Concentrated Species interface and Heat
Transfer interface is synchronized to the one computed in the Single-Phase Flow
interface.

When a Chemistry interface is selected, the Reacting Flow coupling synchronizes the
definition of the thermal conductivity, density, heat capacity, enthalpy and dynamic
viscosity with the other coupled physics interfaces. The reference temperature is taken
from the Heat Transfer 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) or Porous Electrode Coupling 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.

THE REACTING FLOW INTERFACES | 463

 TURBULENT MASS TRANSFER
When a turbulence model is used, the Reacting Flow coupling applies turbulence
modeling for the mass transport in the following manners:

• Turbulent heat transfer and mass transport are added, defined from the turbulent
viscosity and a turbulent Schmidt number (for more information, see Turbulent
Mass Transport Models).
• Temperature and mass transport wall functions. When a turbulence model using
wall functions is used for the fluid flow, the Reacting Flow coupling automatically
adds wall functions for the temperature and mass transport on the same boundaries
(for more information, see Mass Transport Wall Functions).

SETTINGS
The Label is the default multiphysics coupling feature name.

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

The default Name (for the first multiphysics coupling feature in the model) is nirf1.

DOMAIN SELECTION
The Reacting Flow coupling is automatically defined on the intersection of the
selections for the coupled interfaces. When modeling porous media transport a
Porous Medium feature, applied on the same domains, is needed in all coupled transport
interfaces. Reacting Flow coupling supports porous media transport in Fluid flow and
Species transport 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,
Species transport, Chemistry, Heat Transfer lists include all applicable physics interfaces.

464 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT 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 a list to uncouple the node from a physics interface.

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 heat and mass transfer is automatically accounted for (see the settings
in the Turbulence section below). Using Reacting Flow, the heat and 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 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, Species transport, Chemistry and Heat
Transfer 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.

MASS TRANSPORT TURBULENCE MODEL

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

THE REACTING FLOW INTERFACES | 465

 μT
N i, T = – --------- ∇ω i
Sc T

where μT is the turbulent viscosity defined by the flow interface, and the turbulent
Schmidt number, ScT, depends on the Mass transport turbulence model used.

HEAT TRANSFER TURBULENCE MODEL

This section is available when a Heat Transfer interface is selected and the fluid flow
interface uses a turbulence model. Select an option from the Heat transport turbulence
model list: Kays-Crawford (the default), Extended Kays-Crawford, or User-defined
turbulent Prandtl number.

For Extended Kays-Crawford, enter a Reynolds number at infinity Reinf (dimensionless).

For User-defined turbulent Prandtl number, enter a Turbulent Prandtl number prT
(dimensionless).

When the flow interface uses a RANS turbulence model, the conductive heat flux is
defined as

q = – ( k + k T ) ∇T

with the turbulent thermal conductivity defined as

μT Cp
k T = --------------
Pr T

where μT is defined by the flow interface, and PrT depends on the Heat transport
turbulence model. See Turbulent Conductivity for details.

The Turbulence model type used by the fluid flow interface can be displayed by selecting
the Show or Hide Physics Property Settings button at the right of the Fluid flow list.

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.

466 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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 Domain, Boundary, and Pair Nodes for the Transport of
Concentrated Species Interface.

THE REACTING FLOW INTERFACES | 467

 The Reacting Flow in Porous Media
Interfaces
The Battery Design 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. A Porous Material node,
including a Fluid and a Solid subnode, is also added to the component.

The interface can be used for stationary and time-dependent analysis in 2D, 2Daxi and
3D.

468 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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 Porous Medium 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 solutes,
dissolved in a solvent of significantly higher concentration. A Porous Medium feature is
active by default on the entire interface selection.

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. A Porous Material node is also added to the
component.

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 Porous Medium feature
is active by default on the entire interface selection.

The Transport of Concentrated Species in Porous Media interface solves for an arbitrary
number of mass fractions in free and porous media. In the current multiphysics
interface a Porous Medium 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 Chemical Reaction Engineering Module User’s Guide.

THE REACTING FLOW IN POROUS MEDIA INTERFACES | 469

 The Reacting Flow Coupling Feature
For the settings of this feature see The Reacting Flow Coupling Feature in the
Chemical Reaction Engineering Module User’s Guide.

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 Domain, Boundary, and Pair Nodes for the Transport of Diluted Species
Interface section.

TRANSPORT OF CONCENTRATED SPECIES

The available physics features for The Transport of Concentrated Species interface are
listed in the Domain, Boundary, and Pair Nodes for the Transport of Concentrated
Species Interface section.

470 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

The Nonisothermal Reacting Flow
Multiphysics Interfaces
Nonisothermal Reacting Flow is a predefined multiphysics interface, available in the
Battery Design Module, that couples fluid flow and heat transfer with species transport
and reactions.

Selecting an entry in the Chemical Species Transport>Nonisothermal Reacting Flow

branch of the Model Wizard, or Add Physics windows, the following four physics
interfaces are added to the Model Builder:

• Chemistry
• Transport of Concentrated Species
• Laminar Flow, or a turbulent flow equivalent like Turbulent Flow, k-ε.
• Heat Transfer in Fluids

In addition, the Multiphysics node is added, which includes the multiphysics coupling
feature Reacting Flow. The Reacting Flow feature predefines and controls the couplings
between the separate interfaces in order to facilitate set up of models.

In this section:

• The Nonisothermal Reacting Laminar Flow Interface

• The Nonisothermal Reacting Turbulent Flow, k-ε Interface
• The Nonisothermal Reacting Turbulent Flow, k-ω Interface
• The Nonisothermal Reacting Turbulent Flow, SST Interface
• The Nonisothermal Reacting Turbulent Flow, Low Re k-ε Interface
• The Reacting Flow Coupling Feature
• Physics Interface Features

The Nonisothermal Reacting Laminar Flow Interface

The Nonisothermal Reacting Laminar Flow ( ) multiphysics interface is used to
simulate laminar flow and heat transfer coupled to species transport in a gas or liquid.

It combines the Chemistry, Transport of Concentrated Species, Laminar Flow, and Heat
Transfer in Fluids interfaces. The Reacting Flow multiphysics coupling, which is added
automatically, couples fluid flow, heat transfer and mass transfer. The species transport

THE NONISOTHERMAL REACTING FLOW MULTIPHYSICS INTERFACES | 471

 supports both a mixture, where the concentrations are of comparable order of
magnitude, and low-concentration solutes in a solvent.

The multiphysics coupling takes into account the heat of reaction, enthalpy diffusion,
and contributing mass fluxes. In addition, the temperature dependency of the chemical
properties and reactions are accounted for.

The interface can be used for stationary and time-dependent analysis in 2D, 2D axial
symmetry, and 3D.

On the constituent physics interfaces:

The Chemistry interface defines thermodynamic properties and transport properties of

the fluid. Provided that properties of each species have been defined, composition
dependent mixture properties such as the heat capacity, the density, and the heat
conduction are defined. The Chemistry interface also defines reaction rates for species
involved in the chemical reactions added to the system.

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. A Transport Properties feature is active by
default on the entire interface selection

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.

The Heat Transfer interface solves for conservation of energy. A Fluid feature is active
by default on the entire interface selection.

The Nonisothermal Reacting Turbulent Flow, k-ε Interface

The Nonisothermal Reacting Turbulent Flow, k-ε ( ) multiphysics interface is used to
simulate flow in the turbulent regime, heat transfer, and species transport and in a gas
or liquid. This interface requires a license for either the CFD Module or the Heat
Transfer Module.

It combines the Chemistry, Transport of Concentrated Species, Turbulent Flow, k-ε, and
Heat Transfer in Fluids interfaces. The Reacting Flow multiphysics coupling, which is
added automatically, couples fluid flow, heat transfer and mass transfer. The species
transport supports both a mixture, where the concentrations are of comparable order
of magnitude, and low-concentration solutes in a solvent.

472 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

The multiphysics coupling takes into account the heat of reaction, enthalpy diffusion,
and contributing mass fluxes. In addition, the temperature dependency of the chemical
properties and reactions are accounted for.

The interface can be used for stationary and time-dependent analysis in 2D, 2D axial
symmetry, and 3D.

On the constituent physics interfaces:

The Chemistry interface defines thermodynamic properties and transport properties of

the fluid. Provided that properties of each species have been defined, composition
dependent mixture properties such as the heat capacity, the density, and the heat
conduction are defined. The Chemistry interface also defines reaction rates for species
involved in the chemical reactions added to the system.

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. Mass transfer close to walls is modeled using
wall functions

The equations solved by the Turbulent Flow, k-ε interface are the Navier-Stokes
equations for conservation of momentum and the continuity equation for
conservation of mass. Turbulence effects are modeled using the standard two-equation
k-ε model with realizability constraints. Flow close to walls is modeled using wall
functions.

The Heat Transfer interface solves for conservation of energy. A Fluid feature is active
by default on the entire interface selection. Heat transfer close to walls is modeled
using wall functions.

The Nonisothermal Reacting Turbulent Flow, k-ω Interface

The Nonisothermal Reacting Turbulent Flow, k-ω ( ) multiphysics interface is used to
simulate flow in the turbulent regime, heat transfer, and species transport and in a gas
or liquid. This interface requires a license for the CFD Module.

It combines the Chemistry, Transport of Concentrated Species, Turbulent Flow, k-ω, and
Heat Transfer in Fluids interfaces. The Reacting Flow multiphysics coupling, which is
added automatically, couples fluid flow, heat transfer and mass transfer. The species
transport supports both a mixture, where the concentrations are of comparable order
of magnitude, and low-concentration solutes in a solvent.

THE NONISOTHERMAL REACTING FLOW MULTIPHYSICS INTERFACES | 473

 The multiphysics coupling takes into account the heat of reaction, enthalpy diffusion,
and contributing mass fluxes. In addition, the temperature dependency of the chemical
properties and reactions are accounted for.

The interface can be used for stationary and time-dependent analysis in 2D, 2D axial
symmetry, and 3D.

On the constituent physics interfaces:

The Chemistry interface defines thermodynamic properties and transport properties of

the fluid. Provided that properties of each species have been defined, composition
dependent mixture properties such as the heat capacity, the density, and the heat
conduction are defined. The Chemistry interface also defines reaction rates for species
involved in the chemical reactions added to the system.

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. Mass transfer close to walls is modeled using
wall functions

The equations solved by the Turbulent Flow, k-ω interface are the Navier-Stokes
equations for conservation of momentum and the continuity equation for
conservation of mass. The fluid flow turbulence is modeled using the Wilcox revised
k-ω model with realizability constraints. Flow close to walls is modeled using wall
functions.

The Heat Transfer interface solves for conservation of energy. A Fluid feature is active
by default on the entire interface selection. Heat transfer close to walls is modeled
using wall functions.

The Nonisothermal Reacting Turbulent Flow, SST Interface

The Nonisothermal Reacting Turbulent Flow, k-SST ( ) multiphysics interface is used
to simulate flow in the turbulent regime, heat transfer, and species transport and in a
gas or liquid. This interface requires a license for the CFD Module.

It combines the Chemistry, Transport of Concentrated Species, Turbulent Flow, k-SST, and
Heat Transfer in Fluids interfaces. The Reacting Flow multiphysics coupling, which is
added automatically, couples fluid flow, heat transfer and mass transfer. The species
transport supports both a mixture, where the concentrations are of comparable order
of magnitude, and low-concentration solutes in a solvent.

474 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

The multiphysics coupling takes into account the heat of reaction, enthalpy diffusion,
and contributing mass fluxes. In addition, the temperature dependency of the chemical
properties and reactions are accounted for.

The interface can be used for stationary and time-dependent analysis in 2D, 2D axial
symmetry, and 3D.

On the constituent physics interfaces:

The Chemistry interface defines thermodynamic properties and transport properties of

the fluid. Provided that properties of each species have been defined, composition
dependent mixture properties such as the heat capacity, the density, and the heat
conduction are defined. The Chemistry interface also defines reaction rates for species
involved in the chemical reactions added to the system.

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. Mass transfer close to walls is modeled using
wall functions

The equations solved by the Turbulent Flow, k-SST interface are the Navier-Stokes
equations for conservation of momentum and the continuity equation for
conservation of mass. The fluid flow turbulence is modeled using the SST model. The
SST model is a low-Reynolds number model which means that it resolves the velocity,
pressure, and concentrations all the way down to the wall. For that reason this physics
interface is suited for studying mass transfer at high Schmidt numbers. The SST model
depends on the distance to the closest wall, and the interface therefore includes a wall
distance equation.

The Heat Transfer interface solves for conservation of energy. A Fluid feature is active
by default on the entire interface selection. Heat transfer close to walls is modeled
using wall functions.

The Nonisothermal Reacting Turbulent Flow, Low Re k-ε Interface

The Nonisothermal Reacting Turbulent Flow, Low Re k-ε ( ) multiphysics interface is
used to simulate flow in the turbulent regime, heat transfer, and species transport and
in a gas or liquid. This interface requires a license for either the CFD Module or the
Heat Transfer Module.

It combines the Chemistry, Transport of Concentrated Species,

Turbulent Flow, Low Re k-ε, and Heat Transfer in Fluids interfaces. The Reacting Flow

THE NONISOTHERMAL REACTING FLOW MULTIPHYSICS INTERFACES | 475

 multiphysics coupling, which is added automatically, couples fluid flow, heat transfer
and mass transfer. The species transport supports both a mixture, where the
concentrations are of comparable order of magnitude, and low-concentration solutes
in a solvent.

The multiphysics coupling takes into account the heat of reaction, enthalpy diffusion,
and contributing mass fluxes. In addition, the temperature dependency of the chemical
properties and reactions are accounted for.

The interface can be used for stationary and time-dependent analysis in 2D, 2D axial
symmetry, and 3D.

On the constituent physics interfaces:

The Chemistry interface defines thermodynamic properties and transport properties of

the fluid. Provided that properties of each species have been defined, composition
dependent mixture properties such as the heat capacity, the density, and the heat
conduction are defined. The Chemistry interface also defines reaction rates for species
involved in the chemical reactions added to the system.

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. Mass transfer close to walls is modeled using
wall functions

The equations solved by the Turbulent Flow, Low Re k-ε interface are the Navier-Stokes
equations for conservation of momentum and the continuity equation for
conservation of mass. The fluid flow turbulence is modeled using the AKN
low-Reynolds number k-e model. The low-Reynolds number model resolves the
velocity, pressure, and concentrations all the way down to the wall. For that reason this
physics interface is suited for studying mass transfer at high Schmidt numbers. The
AKN model depends on the distance to the closest wall, and the interface therefore
includes a wall distance equation.

The Heat Transfer interface solves for conservation of energy. A Fluid feature is active
by default on the entire interface selection. Heat transfer close to walls is modeled
using wall functions.

The Reacting Flow Coupling Feature

For the settings of this feature see The Reacting Flow Coupling Feature.

476 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

CHEMISTRY
The available physics features for the Chemistry interface are listed in the section
Feature Nodes Available for the Chemistry Interface.

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 CFD Module
User’s Guide.

TURBULENT FLOW
The available physics features for a single-phase flow interface using a turbulence
model, for example the Turbulent Flow, k-ε interface, is listed in the section Domain,
Boundary, Pair, and Point Nodes for Single-Phase Flow in the CFD Module User’s
Guide.

TRANSPORT OF CONCENTRATED SPECIES

The available physics features for the Transport of Concentrated Species interface are
listed in the section Domain, Boundary, and Pair Nodes for the Transport of
Concentrated Species Interface.

HEAT TRANSFER
The available physics features for the Heat Transfer interface are listed in the section
The Heat Transfer Features in the COMSOL Multiphysics Reference Manual.

THE NONISOTHERMAL REACTING FLOW MULTIPHYSICS INTERFACES | 477

 Theory for the Transport of Diluted
Species Interface
The Transport of Diluted Species Interface provides a predefined modeling
environment for studying the evolution of chemical species transported by diffusion
and convection as well as migration due to an electric field. The physics interface
assumes that all species present are dilute; that is, that their concentration is low
compared to a solvent fluid or solid. As a rule of thumb, a mixture containing several
species can be considered dilute when the concentration of the solvent is more than
90 mol%. Due to the dilution, mixture properties such as density and viscosity can be
assumed to correspond to those of the solvent.

When studying mixtures that are not dilute, the mixture and transport properties
depend on the composition, and a different physics interface is recommended. See The
Transport of Concentrated Species Interface in the Chemical Reaction Engineering
Module User’s Guide for more information.

Fick’s law governs the diffusion of the solutes, dilute mixtures, or solutions, while the
phenomenon of ionic migration is sometimes referred to as electrokinetic flow. The
Transport of Diluted Species interface supports the simulations of chemical species
transport by convection, migration, and diffusion in 1D, 2D, and 3D as well as for
axisymmetric components in 1D and 2D.

In this section:

• Adding Transport Through • Mass Balance Equation

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

Note: Some features explained in this section require certain add-on modules. For
details see https://www.comsol.com/products/specifications/

478 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

• Adsorption • Mass Balance Equation for

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

Mass Balance Equation

The default node attributed to the Transport of Diluted Species interface models
chemical species transport through diffusion and convection and solves the mass
conservation equation for one or more chemical species i:

∂c i
------- + ∇ ⋅ J i + u ⋅ ∇c i = R i (6-17)
∂t

Equation 6-17 in its form above includes the transport mechanisms diffusion and
convection. If Migration in Electric Field is activated (only available in some add-on
products), the migration mechanism will be added to the equation as well. See more
details in the section Adding Transport Through Migration.

• ci is the concentration of the species (SI unit: mol/m3)

• Di denotes the diffusion coefficient (SI unit: m2/s)
• Ri is a reaction rate expression for the species (SI unit: mol/(m3·s))
• u is the mass averaged velocity vector (SI unit: m/s)
• Ji is the mass flux diffusive flux vector (SI unit: mol/(m2·s))

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

J i = – D ∇c i (6-18)

An input field for the diffusion coefficient is available.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 479

 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 6-17 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 6-17), Ri represents a
source or sink term, typically due to a chemical reaction or desorption on a porous
matrix. To specify Ri, another node must be added to the Transport of Diluted Species
interface — the Reaction node for example, which includes an input field for specifying
a reaction expression using the variable names of all participating species.

Equilibrium Reaction Theory

The feature Equilibrium Reaction is described in this section. A chemical equilibrium
reaction system is defined by the stoichiometry of the reaction and the relation
between the chemical activities of the chemical species participating in the reaction (the
equilibrium condition).

The kinetics of the reaction is so fast that the equilibrium condition is fulfilled at all
times in all space coordinates.

The equilibrium condition is commonly based on the stoichiometric coefficients,

νi (dimensionless), of the reaction; the species activities of the reacting species
ai (dimensionless); and an equilibrium constant, Keq (1) according to:

ν
∏ ai i
i ∈ products
K eq = ----------------------------------
–ν
∏ ai i
i ∈ reactants

where the species activities are defined as

ci
a i = γ c, i -------
c a0

where ca0 (SI unit: mol/m3) is the standard molarity, and γc,i (dimensionless) an
activity coefficient.

480 | 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:

νi
K eq = ∏ ai
i

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

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

Settings window. For nonunity activity coefficients, a user defined
equilibrium condition can be used.

EQUILIBRIUM REACTIONS AND INFLOW BOUNDARY CONDITIONS

Contradictory constraints arise if the boundary conditions for concentrations or
activities are set so that the domain equilibrium condition is not fulfilled. Special
treatment is therefore needed at Inflow boundaries, where the concentrations are set
for all species in the mass transport interfaces.

One way of avoiding competing constraints on an inflow boundary is to add an

additional reaction coordinate degree of freedom, solved for to create a set of modified
inflow concentrations that fulfill the domain equilibrium condition. The reaction
coordinate gives rise to a concentration shift, which is the offset to the inflow
concentrations provided by the user. The shift for each species obeys the stoichiometry
of the reaction and the equilibrium expression. The modified inflow concentrations are
then used in the boundary conditions for the domain mass transport equations. The
resulting modified inflow concentrations can be seen as the stationary solution for a
batch reactor with the user inflow concentrations as initial concentrations. In addition,
the domain reaction rate degree of freedom of the equilibrium reaction is constrained
to zero on all Inflow boundaries.

EQUILIBRIUM REACTIONS AND CONCENTRATION BOUNDARY

CONDITIONS
No special treatment is made with regards to input concentration values of the
Concentration boundary node. Using this feature, you can explicitly set one or a set of
concentrations, and the equilibrium condition acts on the rest of the concentrations.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 481

 However, there is no solution to the problem if more concentrations than the number
of species minus the number of equilibrium reactions are set using this feature.

EQUILIBRIUM REACTIONS AND TIME-DEPENDENT SIMULATIONS

Spurious oscillations may occur in a time-dependent problem if the initial conditions
do not fulfill the equilibrium condition. Since equilibrium reactions are assumed to be
infinitely fast, the solution is to initialize the problem using an additional study step,
solving for a stationary problem with all nonequilibrium reaction rates set to zero.
Manual scaling of the reaction rate dependent variables is needed in this study step.

Convective Term Formulation

The default node attributed to The Transport of Diluted Species Interface assumes
chemical species transport through diffusion and convection (depending on the
modules licensed, a check box to activate migration is available) and implements the
mass balance equation in Equation 6-17.

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 (6-19)
∂t

∂c
conservative: ----- + ∇ ⋅ ( cu ) = ∇ ⋅ J i + R (6-20)
∂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.

482 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Solving a Diffusion Equation Only
Remove the convection term from Equation 6-19 and Equation 6-20 by clearing the
Convection check box in the Transport Mechanisms section for The Transport of
Diluted Species Interface. The equation then becomes

∂----c-
= ∇ ⋅ Ji + R
∂t

Mass Sources for Species Transport

Note: The features below are only available in a limited set of add-on products. For a
detailed overview of which features are available in each product, visit
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
·
A point source is theoretically formed by assuming a mass injection/ejection, Q c (SI
unit: mol/(m3·s)), in a small volume δV and then letting the size of the volume tend
to zero while keeping the total mass flux constant. Given a point source strength, q· p,c
(SI unit: mol/s), this can be expressed as

· ·
lim
δV → 0  Qc = qp,c (6-21)
δV

An alternative way to form a point source is to assume that mass is injected/extracted

through the surface of a small object. Letting the object surface area tend to zero while
keeping the mass flux constant results in the same point source. For this alternative
approach, effects resulting from the physical object’s volume need to be neglected.

The weak contribution

q· p,c test ( c )
·
is added at a point in the geometry. As can be seen from Equation 6-21, Q c must tend
to plus or minus infinity as δV tends to zero. This means that in theory the
concentration also tends to plus or minus infinity.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 483

 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 6-21 corresponds to a finite

concentration at a point with the effect of the point source spread out over a region
around the point. The size of the region depends on the mesh and on the strength of
the source. A finer mesh gives a smaller affected region but also a more extreme
concentration value. It is important not to mesh too finely around a point source since
this can result in unphysical concentration values. It can also have a negative effect on
the condition number for the equation system.

LINE SOURCE
·
A line source can theoretically be formed by assuming a source of strength Q l,c (SI
unit: mol/(m3·s)), located within a tube with cross section δS and then letting δS tend
to zero while keeping the total mass flux per unit length constant. Given a line source
strength, q· l,c (SI unit: mol/(m·s)), this can be expressed as

· ·
lim
δS → 0  Ql,c = ql,c (6-22)
δS

As in the point source case, an alternative approach is to assume that mass is injected/
extracted through the surface of a small object. This results in the same mass source,
but requires that effects resulting from the physical object’s volume are neglected.

The weak contribution

q· l,c test ( c )

is added on lines in 3D or at points in 2D (which represent cut-through views of lines).

Line sources can also be added on the axisymmetry line in 2D axisymmetry
components. It cannot, however, be added on geometrical lines in 2D since those
represent physical planes.

As with a point source, it is important not to mesh too finely around the line source.

For feature node information, see Line Mass Source and Point Mass
Source.

484 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 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).

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 (6-23)
∂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

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 485

 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.

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.

486 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Modeling and solving for a supporting electrolyte in the Electrostatics or Secondary
Current Distribution interfaces will give a potential distribution that drives the
migration in the Transport of Diluted Species Interface.

The current density vector is proportional to the sum of all species fluxes as expressed
by Faraday’s law:

i = F  zi Ni
i

The electroneutrality condition ensures that there is always a zero net charge at any
position in a dilute solution. Intuitively, this means that it is impossible to create a
current by manually pumping positive ions in one direction and negative ions in the
other. Therefore, the convective term is canceled out to yield the following expression
for the electrolyte current density, where j denotes the supporting species:

 –zj um, j F cj ∇φ
2
i = F (6-24)
j

Equation 6-24 is simply Ohm’s law for ionic current transport and can be simplified to

i = – κ ∇φ (6-25)

where κ is the conductivity of the supporting electrolyte. A current balance gives the
current and potential density in the cell

∇⋅i = 0

which, in combination with Equation 6-25, yields:

∇ ⋅ ( – κ ∇φ ) = 0 (6-26)

Equation 6-26 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 Péclet 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

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 487

 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.

In some cases, the resulting nonlinear equation system can be difficult to converge.
This can happen when the cell Péclet 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

488 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 n ⋅ ( J i + uc i ) = n ⋅ ( uc i, 0 ) (6-27)

Mass Balance Equation for Transport of Diluted Species in Porous

Media

VARIABLY SATURATED POROUS MEDIA

The following equations for the molar concentrations, ci, describe the transport of
solutes in a variably saturated porous medium for the most general case, when the pore
space is primarily filled with liquid but also contain pockets or immobile gas:

∂ θ ∂
( c ) + ∂ ( ρc P, i ) + (θ g c G, i) + u ⋅ ∇c i =
∂t l i ∂t ∂t (6-28)
∇ ⋅ [ ( D D, i + D e, i ) ∇c i ] + R i + S i

On the left-hand side of Equation 6-28, 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 6-28 ci denotes the concentration of species i in the liquid (SI unit: mol/
m3), cP, i the amount adsorbed to solid particles (moles per unit dry weight of the
solid), and cG, i the concentration of species i in the gas phase.

The equation balances the mass transport throughout the porous medium using the
porosity εp, the liquid volume fraction θl; the dry bulk density, ρ = (1 − εs)ρs, and the
solid phase density ρs.

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

θ g = ε p – θ l = ( 1 – s )ε p

On the right-hand side of Equation 6-28, 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 6-28 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 | 489

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

∂c P, i ∂c i ∂ε p ∂c i ∂ε p
∂ ρc = ρK P,i – c P, i ρ s (6-29)
( P, i ) = ρ – c P, i ρ s ∂ t ∂t
∂t ∂ ci ∂ t ∂t

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

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

∂c G, i ∂c i ∂θ g ∂c i ∂θ g
∂ = θ g k G, i + k G, i c i (6-30)
θ g c G, i = θ g + k G, i c i ∂ t ∂t
∂t ∂ c i ∂ t ∂ t

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

SATURATED POROUS MEDIA

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

∂ ε
( c ) + ∂ ( ρc P, i ) + u ⋅ ∇c i = ∇ ⋅ [ ( D D, i + D e, i ) ∇c i ] + R i + S i (6-31)
∂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

490 | 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
εp
u
u a = ---- Unsaturated
θl

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

Figure 6-4: 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 6-28 is written as:

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 491

 ∂ ( θ c ) + ∂ ( ρc ) + ∂ (θ c ) + ∇ ⋅ uc =
P, i ∂ t g G, i
∂t l i ∂t i
(6-32)
∇ ⋅ [ ( 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 6-28.

When using the nonconservative formulation, which is the default, the fluid is assumed
incompressible and divergence free: ∇ ⋅ u = 0. The nonconservative formulation
improves the stability of systems coupled to a momentum equation (fluid flow
equation).

To switch between the two formulations, click the Show button ( ) and
select Advanced Physics Options. In the section Advanced Settings select
either Nonconservative form (the default) or Conservative form. The
conservative formulation should be used for compressible flow.

Diffusion in Porous Media

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

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

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

The tortuosity factor accounts for the reduced diffusivity due to the fact that the solid
grains impede Brownian motion. The interface provides predefined expressions to

492 | 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
τL = θl εp , τG = θg εp

and Bruggeman model

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

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

–1 ⁄ 3
τL = εp

and for the Bruggeman model the tortuosity is defined as

–1 ⁄ 2
τL = εp

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

Dispersion
The contribution of dispersion to the mixing of species typically overshadows the
contribution from molecular diffusion, except when the fluid velocity is very low.

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 rate is low relative to the mechanical
dispersion, except at very low fluid velocities.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 493

 Figure 6-5: Spreading of fluid around solid particles in a porous medium.

The dispersion is controlled through the dispersion tensor DD. The tensor
components can either be given by user-defined values or expressions or derived from
the directional dispersivities.

Using the longitudinal and transverse dispersivities in 2D, the dispersivity tensor
components are (Ref. 9):

2 2
ui uj
D Dii = α L ------ + α T ------
u u

ui uj
D Dij = D Dji = ( α L – α T ) -----------
u

In these equations, DDii (SI unit: m2/s) are the principal components of the
dispersivity tensor, and DDji and DDji are the cross terms. The parameters αL and αT
(SI unit: m) specify the longitudinal and transverse dispersivities; and ui (SI unit: m/
s) stands for the velocity field components.

In order to facilitate modeling of stratified porous media in 3D, the tensor formulation
by Burnett and Frind (Ref. 10) can be used. Consider a transverse isotropic media,
where the strata are piled up in the z direction, the dispersivity tensor components are:

494 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 2 2 2
u v w
D Lxx = α 1 ------ + α 2 ------ + α 3 -------
u u u
2 2 2
v u w
D Lyy = α 1 ------ + α 2 ------ + α 3 -------
u u u
2 2 2
w u v
D Lzz = α 1 ------- + α 3 ------ + α 3 ------
u u u (6-33)
uv
D Lxy = D Lyx = ( α 1 – α 2 ) -------
u
uw
D Lxz = D Lzx = ( α 1 – α 3 ) --------
u
vw
D Lyz = D Lzy = ( α 1 – α 3 ) --------
u

In Equation 6-33 the fluid velocities u, v, and w correspond to the components of the
velocity field u in the x, y, and z directions, respectively, and α1 (SI unit: m) is the
longitudinal dispersivity. If z is the vertical axis, α2 and α3 are the dispersivities in the
transverse horizontal and transverse vertical directions, respectively (SI unit: m).
Setting α2 = α3 gives the expressions for isotropic media shown in Bear (Ref. 9 and
Ref. 11).

Adsorption
As species travel through a porous medium they typically attach to (adsorb), and
detach (desorb) from the solid phase, which slows chemical transport through the
porous medium. Adsorption and desorption respectively reduces or increases species
concentrations in the fluid. The adsorption properties vary between chemicals, so a
plume containing multiple species can separate into components (Ref. 6). The
Adsorption feature includes four predefined and one user defined relationships to
predict the solid concentrations, cPi from the concentration in the liquid phase, ci:

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 495

 KL c
c P = c Pmax -------------------- Langmuir
1 + KL c
c N
c P = K F  -------- Freundlich
 c ref
bT c (6-34)
c P = c Pmax ---------------------------------------------- Toth
N 1 ⁄ NT
( 1 + ( bT c ) T )
KB c0 c
c P = -------------------------------------------------------------- BET
( c S – c )  1 + ( K B – 1 ) -----
c
 c S

The above equations contains the following parameters:

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

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

These predefined expressions are adsorption isotherms that describe the amount of
species sorbed to the solid. Defined at equilibrium, the switch between liquid and solid
phases is instantaneous.

Using a Species Source feature, arbitrary expressions can be entered to define, for
example, nonequilibrium and temperature-dependent adsorption laws, including
those set out by Fetter (Ref. 7) and Bear and Verruijt (Ref. 8).

The retardation factor, RF, describes how adsorption slows the solute velocity, uc,
relative to the average linear velocity of the fluid, ua, as in

ρ b ∂c P ua
RF = 1 + ----- -------- = -----
θ ∂c uc

If the contaminant moves at the average linear velocity of the fluid for RF = 1. For
RF > 1, the contaminant velocity is lower than the fluid velocity owing to residence
time on solids.

496 | 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 θ. Similarly, solid phase reaction
expressions include the bulk density, ρb, and gas phase reactions include the gas
volume fraction, av.

The following expressions define some common types of reactions:

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

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

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

Ea ( T – TR )
ζ T = ζ R exp ------------------------------ (6-35)
R u TT R

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 497

 In Equation 6-35, T denotes the current absolute temperature, TR denotes the
reference absolute temperature, Ea is the activation energy, and Ru is the universal gas
constant.

Mass Transport in Fractures

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

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

κ
u = --- ∇ t p
μ

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

The equation to solve for mass transport of species ci in a thin fracture, embedded in
a porous media, is derived from Equation 6-28. The resulting equation is:

∂ρ b c P, i ∂ε p c i
d fr  ------------------ + ------------- + ∇ t ⋅ ( D e, i ∇ t c i ) + u ⋅ ∇ t c i = d fr R i + d fr S i + n 0 (6-36)
∂t ∂t

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

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

∇c i = ∇ n c i + ∇ t c i

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

∇c i = ∇ t c i

498 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

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

See Fracture for more information about the boundary feature solving
Equation 6-36. See The Transport of Diluted Species in Fractures
Interface 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 Resour. 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 | 499

 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.

500 | 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 6-37 then describes the mass transport for an individual species:

∂ ρω
( i ) + ∇ ⋅ ( ρω i u ) = – ∇ ⋅ j i + R i (6-37)
∂t

where, ρ (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:

• ωi 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 6-38 for
the conservation of mass

THEORY FOR THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 501

 ∂ρ
+ ∇ ⋅ ( ρu ) = 0 (6-38)
∂t

assuming that

Q Q Q

 ωi = 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:

ρ ∂ ( ω i ) + ρ ( u ⋅ ∇ )ω i = – ∇ ⋅ j i + R i (6-39)
∂t

Q − 1 of the species equations are independent and possible to solve for using
Equation 6-39. 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:

ω1 = 1 –  ωi (6-40)
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 = – ρω i (6-41)
k=1

In Equation 6-41:
˜
• D 2
ik (SI unit: m /s) are the multicomponent Fick diffusivities

• 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)

502 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 Q
1
d k = -------------- ∇p k – ω k ∇p – ρ k g k + ω k
cR g T  ρl gl (6-42)
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
• ρk (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.

When an external force applies equally to all species (such as for gravity),
the last two terms disappear.

As can be seen in Equation 6-41 and Equation 6-42, 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 – ω k ) ∇p – ρω k g k + ω k
p  ρωl gl (6-43)
l=1

The mole fraction xk is given by

ωk
x k = -------- M (6-44)
Mk

and the mean molar mass M (SI unit: kg/mol) by

Q
1- ωi
----
M
=  ------
Mi
-
i=1

THEORY FOR THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 503

 When using the Maxwell–Stefan diffusion model, the transport equations for the
species’ mass are

Q
 
ρ ∂ ( ω i ) + ρ ( u ⋅ ∇ )ω i = ∇ ⋅  ρω i ˜ d + DT ∇ T-
∂t 
D ik k i -------
T 
+ Ri
 k=1 
(6-45)
Q
1
d k = ∇x k + --- ( x k – ω k ) ∇p – ρω k g k + ω k
p  ρωl gl
l=1

Multicomponent Diffusivities
˜
The multicomponent Fick diffusivities, D ik , are needed to solve Equation 6-45. 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 ˜ ,
---------- = – ω i ω k ---------------------------------------- , ( B ) = D kj ij i≠j (6-46)
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 6-46 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:

ω1 ( ω2 + ω3 ) ω2 ( ω1 + ω3 ) ω 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

504 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

For four components or more, COMSOL Multiphysics obtains the multicomponent
Fick diffusivities numerically through matrix inversion derived from the matrix
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 (6-47)
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 6-47 are defined as

–1
N ij = ( P ) ij (6-48)

where P−1 is the inverse of a matrix P defined as

ωi ωj ˜
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 6-47 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 =    Dij 

i = 1  j = i+1 

This definition for g works well in most cases. In rare cases, it might be
necessary to change the value to obtain convergence.

THEORY FOR THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 505

 Because the multicomponent Fick diffusivity matrix is symmetric, it is sufficient to
˜
apply Equation 6-48 to the upper triangle elements of D . The remaining elements are
obtained by swapping the indices in the matrix.

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 = – ρ i D i --------- (6-49)
xi

Here ρi is the density, and xi the mole fraction of species i. Using the definition of the
species density and mole fraction

ωi
ρ i = ρω i , x i = ------- M
Mi

Equation 6-49 can be expressed in terms of the mass fractions (ωi) in the manner of

m ∇M
j md, i = –  ρD i ∇ω i + ρω i D i ---------
m
M

Using Equation 6-49 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 – ωi
D i = -------------------------- (6-50)
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* ∇ω i m*
j md, i = – ρ i D i ---------- = – ρD i ∇ω i (6-51)
ωi

506 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

For this assumption, using Equation 6-51 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 ωk
k ≠ i --------
D ik 1 – ω i k ≠ i D ik
N N
----------- = - + --------------- --------- (6-52)
m*
Di

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 jmd, i = i = 1 ρωi ( ud,i + uc )

N N
= 0 (6-53)

Hence the correction velocity is:

i = 1 ωi ud,i
N
uc = – (6-54)

Here ud,i is the diffusion velocity resulting from the flux assumption in Equation 6-49
or Equation 6-51. Note that the correction velocity is a constant correction (same for
all species), but varies in space.

Using the correction velocity together with Equation 6-49 (flux proportional to the
mole fraction gradient), the resulting diffusive flux is

m ∇M Mi
i = 1 ------
m N m
j md, i = – ρD i ∇ω i – ρω i D i --------- + ρω i - D ∇x i (6-55)
M M i

THEORY FOR THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 507

 If instead Equation 6-51 is used (flux proportional to the mass fraction gradient), the
resulting diffusive flux is

i = 1 Di
m* N m*
j md, i = – ρD i ∇ω i + ρω i ∇ω i (6-56)

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 -------- + ρω i z i u m, i F ∇φ
 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
• φ (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 = – ρ i D i, kl --------- (6-57)
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 = – ρD i, kl ∇ω i (6-58)
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,

508 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 F 0
D i, kk = D i

These coefficients are typically more readily available compared to the binary diffusion
diffusivities, especially for liquid mixtures.

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 = – ρD i, kl ∇ω i – ρω i D i, kl --------- + ρω i - D ∇x (6-59)
M M i, kl i

when using Equation 6-57 and

i = 1 Di, kl ∇ωi
F N F
j md, i = – ρD i, kl ∇ω i + ρω i (6-60)

when instead using Equation 6-58.

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 ωi. But a reactant, ωr, can physically only be
consumed if ωr > 0 and a product, ωk, can only be formed if ωk < 1. The Reaction

THEORY FOR THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 509

 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 ωi is replaced by

c c c c
1 Ri – Ri 1 Ri + Ri
R i = --- -------------------------------- max ( ω i, 0 ) + --- -----------------------------------------
- max ( 1 – ω i, 0 ) (6-61)
2 max ( ω , ω ) dl 2 max ( 1 – ω , ω dl )
i i i i

The first term on the right hand side of Equation 6-61 is active if Ric < 0, that is if ωi
is a reactant. The reaction rate contribution, Ri, is equal to the “core” reaction rate,
Ric, as long as ωi > ωidl. As ωi approaches zero, the regularization damps out negative
Ric and for ωi < 0, Ri for reactant ωi is equal to zero.

The second term on the right hand side of Equation 6-61 is active if Ric > 0, that is if
ωi is a product. The reaction rate contribution, Ri, is equal to the “core” reaction rate,
Ric, as long as ωi < 1−ωidl. As ωi approaches one, the regularization damps out
positive Ric and for ωi > 1, Ri for product ωi is equal to zero.

The damping limits, ωidl, 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.

510 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

Theory for the Electrophoretic
T r a ns po r t Interface
The Electrophoretic Transport Interface models transport of charged and uncharged
species, and in addition sets up a charge balance equation for the electrolyte potential.

The species concentrations are denoted, ci (SI unit: mol/m3), and the potential, φ l
(SI unit: V).

The species are transported by diffusion, migration, and (optionally) convection

according the Nernst–Planck set of equations. The total flux of species i is denoted Ni
(SI unit: mol/(m2·s)) according to

N i = – D i ∇c i – z i u m, i Fc i ∇φ l + uc i = J i + uc i (6-62)

where Di (SI unit: m2/s) is the diffusion coefficient, zi (1) the corresponding charge,
um,i (SI unit: s·mol/kg) the mobility and u (SI unit: m/s) the velocity vector. Ji
denotes the molar flux relative to the convective transport (SI unit: mol/(m2·s)). For
a detailed description of the theory of these equations and the different boundary
conditions, see Theory for the Transport of Diluted Species Interface.

CHARGE BALANCE EQUATION

2
The current vector, il (A/m ), is defined as

il =  zi Ni (6-63)
i

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

The governing equation for the electrolyte potential is

∇ ⋅ il = Ql (6-64)

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.

THEORY FOR THE ELECTROPHORETIC TRANSPORT INTERFACE | 511

 PROTON AND HYDROXIDE CONCENTRATIONS AND ELECTRONEUTRALITY
Assuming the total number of species to be N + 2, the assumption of electroneutrality
is

N+2

 zi ci = 0 (6-65)
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 (6-66)

This reaction is fast, following the equilibrium relation

2 –6
c H + c OH - = K w × 1 mol dm (6-67)

– 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 (6-68)
i=1

Combining these two equations results in the following algebraic expressions for the
concentrations of H+ and OH-.

2
Σ Σ 2 –6
c H + = – --- + ------ + K w × 1 mol dm (6-69)
2 4

and

2
Σ Σ 2 –6
c OH - = --- + ------ + K w × 1 mol dm (6-70)
2 4

where

Σ =  zi ci (6-71)
i=1

512 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

MASS BALANCE EQUATIONS FOR DISSOCIATION SPECIES
Assume a set of species Si describing k dissociation steps from

+ z +k–1
z +k z +k–1 + [ H ] [ S k0– 1 ]
S k0 ↔ S k0– 1 +H K a, 1 = ----------------------------------------
z0 + k
(6-72)
[ Sk ]

to

+ z
z +1 z + [ H ] [ S 00 ]
S k0 ↔ S 00 + H K a, k = -------------------------
z +1
- (6-73)
[ 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 represent 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
(6-74)

∏ 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
(6-75)

if l > m.

Setting m = i and denoting the flux of species i by Ni using equation Equation 6-62,
the mass balance equation for the concentration ci of each subspecies i in the
dissociation chain is

δc
-------i + ∇ ⋅ N i = R eq, i, k – i – R eq, i, k – i + 1 + R i (6-76)
δt

where Req,i,j is the reaction source stemming from the jth dissociation step (with
Req,i,k+1 = 0), and Ri any additional reaction sources.

THEORY FOR THE ELECTROPHORETIC TRANSPORT INTERFACE | 513

 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

k k
δc i
 ------ 
 -
 δt + ∇ ⋅ N i =  Ri (6-77)
i=0 i=0

AVERAGE IONIZATION FORMULATION FOR LARGE MOLECULES

Large protein molecules are typically subject to a large number of dissociation steps.

As an alternative way to a long chain of dissociation steps for describing protein

transport, one can instead formulate the protein transport based on the average
number of protons ν (1) removed from the molecule. ν is typically provided as a
function of pH, based on experimental data. The average charge of the species then is
z = z 0 – ν , so that the flux of the species is written as:

N i = – D∇c i – zu m Fc i ∇φ l + uc i (6-78)

and similarly the addition to the charge neutrality condition is zc i .

When considering the contribution to the current and the charge balance equation one
2 2
needs to take into account that the squared average charge, z = ( z 0 – ν ) , is not
2 2 2 2 2 2
equal to the “average squared charge”, z = z 0 + 2z 0 ν + ν = z – ν + ν (Ref. 1).

The addition to the current density vector is

2
i l = … – F ( zD i ∇c i + z u m c i ∇φ l ) (6-79)

The average number of protons removed from the proton typically depends on the
pH. If the average number of removed protons depend only on the pH, the averaged
squared number of protons removed can be written as

2 d ν ν2
ν = – cH+ + (6-80)
d c H+

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

2 2
z = – c H+ d ν + z = – cH+ d z + z
2
(6-81)
d cH+ d cH+

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

514 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

 kT
r = --------------- (6-82)
6πμD

where is the μ (SI unit: Pa·s) is the dynamic viscosity and k the Boltzmann constant.

For small molecules, one frequently uses the Nernst–Einstein relation between the
diffusivity and the mobility

D
u m = -------- (6-83)
RT

For larger molecules, such as proteins, the mobility may instead be calculated based on
the Debye–Hückel–Henry expression (Ref. 2 ) according to

ef ( κr ) Df ( κr )
u m = ------------------------------------ = ------------------------------ (6-84)
6πμF ( 1 + κr ) RT ( 1 + κr )

where κ (1/m) is the Debye parameter, which depends on the ionic strength of the
solution, is defined for ideal solutions as

2 N
2e N A
 zi ci
2 2
κ = ----------------- (6-85)
εε 0 kT
i=1

where ε is the dielectric constant of the fluid and ε0 the permittivity of free space.
2
( z should be used if available in the formula above when calculating the ionic
strength).

The function f above is based on a sigmoidal function so that it ranges from 1 for
κr = 0 to 1.5 for κr = ∞ . Note that the Debye-Hückel-Henry expression
approaches the Nernst–Einstein mobility as r → 0 .

For larger molecules (macro ions), where the distance between the charges is large
compared to 1/κ, the Linderstrøm-Lang approximation postulates a smaller
contribution of to the ionic strength so that the z-valent ion behaves as a monovalent
ion with a z-fold concentration. For an assemble of N − M smaller molecules and M
macro ions, the Debye parameter then is defined as

N–M N
2e N A  
2
κ = -----------------    abs(z i)c i
2 2
zi ci + (6-86)
εε 0 kT
 i=1 i = N–M+1 

THEORY FOR THE ELECTROPHORETIC TRANSPORT INTERFACE | 515

 REFERENCES
1. R.A. Mosher, D.A. Saville, and W. Thormann, The Dynamics of Electrophoresis,
VCH Verlagsgesellschaft mbH, Weinheim, Germany, 1992.

2. R.A. Mosher, P. Gebauer, J. Caslavska, and W. Thormann, “Computer Simulation

and Experimental Validation of the Electrophoretic Behavior of Proteins. 2. Model
Improvement and Application to Isotachophoresis,” Anal. Chem., vol. 64, pp. 2991–
2997, 1992.

516 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

T he o r y f o r t he S u rface R eact i on s
Interface
The Surface Reactions Interface solves for an arbitrary number of surface
concentrations, cs,i (SI unit: mol/m2), referring to species adsorbed on a reactive
surface, and an arbitrary number of bulk concentrations cb,k (SI unit: mol/m3),
referring to the species in the solid material that constitutes the bulk of the reactive
surface.

In this section:

• Governing Equations for the Surface Concentrations

• Governing Equations for the Bulk Concentrations
• ODE Formulations for Surface Concentrations
• Surface Reaction Equations on Deforming Geometries
• Reference for the Surface Reactions Interface

Governing Equations for the Surface Concentrations

Transport of adsorbed species occurs in the tangential direction along the surface. The
Surface Reactions interface models the tangential flux in the surface dimension, the
surface molar flux, Nt,i (SI unit: mol/(m·s)) (the subscript t refers to the tangential
direction), as governed by diffusion according to Fick’s law:

N t, i = – D s, i ∇ t c s, i

where Ds,i (SI unit: m2/s) is the surface diffusion coefficient for species i.

The governing equation for the surface concentrations is written as:

∂c s, i
= – ∇ t ⋅ N t, i + R s , i (6-87)
∂t

where Rs,i (SI unit: mol/(m2·s)) is the sum of all sources due to surface reactions and
adsorption/desorption phenomena.

Of frequent interest for surface reaction kinetics are the fractional surface coverages, θi
(dimensionless), of the species (with index i).

THEORY FOR THE SURFACE REACTIONS INTERFACE | 517

 Writing the density of sites of the surface as Γs (SI unit: mol/m2) and the site
occupancy number for each species as σi (dimensionless), the surface coverages can be
calculated from:

σ i c s, i
θ i = --------------
Γs

(The site occupancy number accounts for the situation when a large species covers
more than one site on the surface.)

For the case of monolayer adsorption, the sum of all fractional coverages of free and
adsorbed sites is unity, and hence the fraction of free sites on the surface, θ*, can be
calculated from:

θ* = 1 –  θi
i

Governing Equations for the Bulk Concentrations

BULK SPECIES RATES AND GROWTH VELOCITY

The reaction rate for a bulk species of index k, being added to the bulk due to surface
reactions is defined as Rb,k (SI unit: mol/(s·m2)).

The reaction rate in mass basis, rb,k (SI unit: kg/(s·m2)) for species k, is given by:

r k = M k R b, k

with Mk (SI unit: kg/mol) being the molar mass of the species.

Based on this, the species contribution to the bulk growth velocity, vk (SI unit: m/s),
is given by:

r b, k
v b, k = ----------
ρk

where ρk is the species density (SI unit: kg/m3).

TOTAL RATES AND VELOCITY

To get the corresponding total values, a summation for all bulk species is made
according to:

518 | 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 (6-88)
∂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 | 519

 leading to the bulk thickness sb,k (SI unit: m) of species k according to:

m b, k
s b, k = -------------
ρk

TOTAL BULK QUANTITIES

The total bulk concentration is calculated according to:

c b, tot =  c b, k
k

The deposited total mass, mb,tot (SI unit: kg/m2) is

m b, tot =  m b, k
k

and the total bulk thickness, stot (SI unit: m) is

s b, tot =  sk
k

FRACTIONAL QUANTITIES
The fractional bulk concentration, bulk mass, and thickness (all dimensionless) are
calculated according to:

c b, k
c b, frac, k = -------------
c b, tot

m b, k
m b, frac, k = ----------------
m b, tot

s b, k
s b, frac, k = -------------
s b, tot

ODE Formulations for Surface Concentrations

The surface of a 1D geometry has a 0 dimension, hence no surface transport can be
modeled and the governing equation is reduced to an ODE:

520 | 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 6-87
and Equation 6-88, 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 6-87 and Equation 6-88, respectively:

∇ t ⋅ ( c s, i v t, mesh )

∇ t ⋅ ( c b, k v t, mesh )

THEORY FOR THE SURFACE REACTIONS INTERFACE | 521

 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.

522 | 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

 νox Sox + ne  νred Sred

-
⇔
ox red

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

In this section:

• Molar Sources and Sinks

• Mass Sources and Sinks

Molar Sources and Sinks

The molar species fluxes, Ni (SI unit: mol/(m2·s)), perpendicular to an
electrode-electrolyte interface are calculated by summing all the flux contributions
from the electrode reactions, of index m, according to Faraday’s law:

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

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

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

Ni = Ni ⋅ n

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

THEORY FOR THE COUPLING OF MASS TRANSPORT TO ELECTROCHEMICAL REACTIONS | 523

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

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

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

Mass Sources and Sinks

To compute the mass flux of a species, ni (SI unit: kg/(m2·s)), the molar flux is
multiplied by the molar mass, Mi (SI unit: kg/mol), resulting in

ni ⋅ n = Mi Ni

for a mass flux boundary, and

R i, mass = M i R i, molar

for a porous source term.

In the Transport of Concentrated Species interface, where a nonconservative

formulation of the flux equations are used, the source term is corrected for the mass
change in the species transporting phase according to

R w i, nonconservative = M i R i, molar – w i  Mi Ri, molar (6-89)

i

Equation 6-89 is for a domain source only, the flux expression over a
boundary is not changed for a nonconservative formulation.

524 | 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:

ω i – nojac ( ω i )
ρ ------------------------------------
Δt̃

is added to the left-hand side of the mass fraction equations. Here ρ is the fluid mixture
density, ωi is the mass fraction (dimensionless) of species i, and Δt̃ is the pseudo time
step. Since ωi−nojac(ωi) 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 Δt̃ .

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 | 525

 n ⋅ ( j i + ρω i u ) = r s,i M i (6-90)

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 ⋅ ρu s =  rs,i Mi (6-91)
i=1

referred to as the Stefan velocity, here denoted us. To reach Equation 6-91 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 6-91 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 ⋅ ρu s =  n ⋅ ( j0, i + ρω0, i u ) (6-92)

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.

526 | CHAPTER 6: CHEMICAL SPECIES TRANSPORT INTERFACES

The resulting Stefan velocity based on mass transport boundary conditions is
computed as:

 n ⋅ j 0, i
i=1
n ⋅ u s = ------------------------------------
- (6-93)
N
 
ρ  1 –  ω i, 0
 i 

Using a Reacting Flow interface, the Stefan velocity, defined in the manner of
Equation 6-93, 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 (6-94)
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 –ν r ν
rj = kj ∏ c i ij – k j ∏ c i ij (6-95)
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 νij, 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 | 527

 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)α − 1/s, where α is the order of the reaction (with
respect to the concentrations).

528 | 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
• Theory for the Laminar Flow and Creeping Flow Interfaces
• Theory for the Darcy’s Law Interface
• Theory for the Free and Porous Media Flow Interface
• Theory for the Brinkman Equations Interface
• Theory for the Coupling of Fluid Flow to Electrochemical Reactions

| 529
 The Laminar Flow and Creeping Flow
Interfaces
In this section:

• The Creeping Flow Interface

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

• Theory for the Laminar Flow and Creeping Flow Interfaces

In the COMSOL Multiphysics Reference Manual, see Table 2-4 for links to common
sections such as Discretization, Consistent Stabilization, Inconsistent Stabilization, and
Advanced Settings sections, some of them accessed by clicking the Show button ( )
and choosing the applicable option. You can also search for information: press F1 to
open the Help window or Ctrl+F1 to open the Documentation window.

The Creeping Flow Interface

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

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

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

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

530 | CHAPTER 7: FLUID FLOW INTERFACES

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

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

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

The Laminar Flow Interface

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

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

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

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

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

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 531

 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.

532 | CHAPTER 7: FLUID FLOW INTERFACES

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

Porous Media Domains

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

Porous Treatment of No Slip Condition

Porous treatment of no slip condition is available when Enable porous media domains is
activated. It controls how the No Slip condition on Wall boundaries and Interior Wall
boundaries adjacent to Porous Medium should be treated. The options are Standard no
slip formulation (default) and Porous slip. The latter option provides a unified treatment
when the porous matrix is fully resolved as well as when it is under-resolved ensuring
a smooth transition between regions with different resolutions; see No Slip under Wall.

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

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

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

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

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 533

 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.

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

534 | CHAPTER 7: FLUID FLOW INTERFACES

because by using it you no longer solve the original problem. By default, the Isotropic
diffusion check box is not selected because this type of stabilization adds artificial
diffusion and affects the accuracy of the original problem. However, this option can be
used to get a good initial guess for underresolved problems.

If required, select the Isotropic diffusion check box and enter a Tuning parameter δid as
a scalar positive value. The default value is 0.25 (a reasonable value to start with is
roughly 0.5 divided by the element order). A higher value adds more isotropic
diffusion.

• Numerical Stability — Stabilization Techniques for Fluid Flow

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

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

When Use pseudo time stepping for stationary equation form is set to Automatic from
physics or On, a CFL number expression should also be defined. For the default Automatic
option, the local CFL number (from the Courant–Friedrichs–Lewy condition) is
determined by a PID regulator.

The Use Block Navier–Stokes preconditioner in time dependent studies check box under
Linear solvers is available when the Compressibility option is set to Incompressible flow.
When this check box is selected, the default solver for time dependent study steps will
use the Block Navier–Stokes preconditioner in iterative solvers for the velocity and

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 535

 pressure. Using this preconditioner may result in shorter solution times for large time
dependent problems with high Reynolds numbers.

• Pseudo Time Stepping for Laminar Flow Models

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

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

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

For 2D axisymmetric components, COMSOL Multiphysics takes the axial

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

In the COMSOL Multiphysics Reference Manual, see Table 2-4 for links to common
sections and Table 2-5 to common feature nodes. You can also search for information:
press F1 to open the Help window or Ctrl+F1 to open the Documentation window.

For a detailed overview of the functionality available in each product, visit

https://www.comsol.com/products/specifications/

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.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 537

 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 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.

538 | CHAPTER 7: FLUID FLOW INTERFACES

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

FLUID PROPERTIES

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

Dynamic Viscosity
The Dynamic viscosity μ describes the relationship between the shear rate and the shear
stresses in a fluid. Intuitively, water and air have low viscosities, and substances often
described as thick (such as oil) have higher viscosities.

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

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

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

Initial Values
The initial values serve as initial conditions for a transient simulation or as an initial
guess for a nonlinear solver in a stationary simulation. Note that for a transient
compressible-flow simulation employing a material for which the density depends on

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 539

 the pressure (such as air), discontinuities in the initial values trigger pressure waves
even when the Mach number is small. The pressure waves must be resolved and this
puts a restriction on the time step.

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

When Include gravity is selected and Use reduced pressure not selected in the interface
Physical model section, the Compensate for hydrostatic pressure approximation (named
Compensate for hydrostatic pressure for compressible flows) check box is available and
selected by default. When it is selected, the hydrostatic pressure is automatically added
to the pressure entered in p user input.

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

BOUNDARY CONDITION
Select a Boundary condition for the wall.

• No Slip • Leaking Wall

• Slip • Navier Slip

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

The option for Porous treatment of no slip condition is available when Enable porous
media domains is activated in the Physical Model section in the settings for the main
physics interface node. It specifies how Wall boundaries and Interior Wall boundaries
internal to porous domains are treated. When the default Standard no slip formulation
is chosen, a common no slip condition is applied on all solid walls. When Porous slip is
chosen, a blending analytic expression is instead applied on the corresponding wall
boundaries adjacent to the porous medium domain. It results in a no slip condition in
case the porous length scale is fully resolved by the mesh and a slip condition in the

540 | CHAPTER 7: FLUID FLOW INTERFACES

opposite limit when the mesh is much coarser than the porous scale. A smooth
transition between these limits is ensured. Note that the interpretation and usage of
non-zero slip at the wall is the same as in the Navier slip boundary condition. By
default, Velocity formulation is on and the treatment is based on an approximate
reconstruction of the far field pressure gradient using the slip velocity at the wall. If the
Pressure-gradient formulation is chosen, the local pressure gradient at the wall is
employed.

Slip
The Slip option prescribes a no-penetration condition, u·n = 0. It is implicitly assumed
that there are no viscous effects at the slip wall and hence, no boundary layer develops.
From a modeling point of view, this can be a reasonable approximation if the main
effect of the wall is to prevent fluid from leaving the domain.

Leaking Wall
This boundary condition may be used to simulate a wall where fluid is leaking into or
leaving the domain with the velocity u = ul through a perforated wall. The
components of the Fluid velocity ul on the leaking wall should be specified.

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

μ
K nt = – --- u slip
β

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

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

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

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

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

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 541

 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 with the
surface sliding in a tangential direction. A velocity is prescribed at the wall and the
boundary itself does not have to actually move relative to the reference frame.

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

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

542 | CHAPTER 7: FLUID FLOW INTERFACES

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, Fully developed flow,
and Pressure. After selecting a Boundary Condition from the list, a section with the same
or a similar name displays underneath. For example, if Velocity is selected, a Velocity
section, where further settings are defined, is displayed.

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

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

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 543

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

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

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

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

544 | CHAPTER 7: FLUID FLOW INTERFACES

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
in integration coupling operators do not include this scaling automatically. Such results
should be appropriately scaled when comparing them with the specified mass flow.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 545

 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. The exception is gravity when the
Include gravity setting is selected in the physics interface settings. Unless Use reduced
pressure is also selected, an option to Compensate for hydrostatic pressure or
Compensate for hydrostatic pressure approximation becomes available. It is selected per
default and should only be deselected if the inlet normal is aligned with the gravity
force and you want to specify an average pressure that includes the hydrostatic
pressure.

A fully developed flow boundary cannot be adjacent to any Interior Wall feature.

546 | CHAPTER 7: FLUID FLOW INTERFACES

CONSTRAINT SETTINGS
This section is displayed by clicking the Show button ( ) and selecting Advanced
Physics Options.

• Prescribing Inlet and Outlet Conditions

• Normal Stress Boundary Condition

Fully Developed Flow (Inlet)

Outlet
This condition should be used on boundaries for which there is a net outflow from the
domain. To obtain a numerically well-posed problem, it is advisable to also consider
the Inlet conditions when specifying an Outlet condition. For example, if the velocity
is specified at the inlet, the pressure may be specified at the outlet, and vice versa.
Specifying the velocity vector at both the inlet and the outlet may cause convergence
difficulties. Selecting appropriate outlet conditions for the Navier–Stokes equations is
a nontrivial task. Generally, if there is something interesting happening at an outflow
boundary, the computational domain should be extended to include this
phenomenon.

BOUNDARY CONDITION
The available Boundary condition options for an outlet are Pressure, Fully developed flow,
and Velocity.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 547

 PRESSURE CONDITIONS
This option specifies the normal stress, which in most cases is approximately equal to
the pressure. The tangential stress component is set to zero.

• For incompressible flow, the Pressure list has two options, Static and Total. For
weakly compressible and compressible flow, the static pressure should be specified
in the text field.
- If Pressure is Static, and the reference pressure pref, defined at the physics
interface level, is equal to 0, the value of the pressure p0, at the boundary, is the
absolute pressure. Otherwise, p0 is the relative pressure at the boundary.
- If Pressure is Total, the Average check box is available and selected by default to
prescribed the averaged total pressure in the weak forms. If it is cleared, the total
pressure is imposed pointwise.
When Include gravity is selected and Use reduced pressure not selected in the interface
Physical model section, the Compensate for hydrostatic pressure approximation (named
Compensate for hydrostatic pressure for incompressible flows) check box is available and
selected by default. When it is selected, the hydrostatic pressure is automatically added
to the pressure entered in p0 user input.

• The Normal flow option changes the no tangential stress condition to a no tangential
velocity condition. This forces the flow to exit (or enter) the domain perpendicularly
to the outlet boundary.
• The Suppress backflow check box is selected by default. This option adjusts the outlet
pressure in order to reduce the amount of fluid entering the domain through the
boundary.

VELOCITY
See the Inlet node Velocity section for the settings.

FULLY DEVELOPED FLOW

This boundary condition is applicable when the flow exits the domain into a long pipe
or channel, at the end of which a flow profile is fully developed.

The channel can be thought of as a virtual extrusion of the outlet cross section. The
outlet boundary must hence be flat in order for the fully developed flow condition to
work properly. In 2D axisymmetric models, the outlet normal must be parallel to the
symmetry axis.

548 | CHAPTER 7: FLUID FLOW INTERFACES

Select an option to control the flow rate at the outlet:

• Average velocity, Uav.

• Flow rate, V0. Two-dimensional models also require an Entrance thickness, Dz,
which is the out-of-plane thickness of the extruded entrance channel.
• Average pressure, Pav. Observe that Pav is the average pressure on the outflow.

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

The fully developed flow condition requires any volume force to be approximately
aligned with the normal of the outlet boundary. The exception is gravity when the
Include gravity setting is selected in the physics interface settings. Unless Use reduced
pressure is also selected, an option to Compensate for hydrostatic pressure or
Compensate for hydrostatic pressure approximation becomes available. It is selected per
default and should only be deselected if the outlet normal is aligned with the gravity
force and you want to specify an average pressure that includes the hydrostatic
pressure.

A fully developed flow boundary cannot be adjacent to any Interior Wall feature.

CONSTRAINT SETTINGS
This section is displayed by clicking the Show button ( ) and selecting Advanced
Physics Options.

Prescribing Inlet and Outlet Conditions

Fully Developed Flow (Outlet)

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 549

 Symmetry
This node provides a boundary condition for symmetry boundaries. It should only be
used when the geometry and expected solution have mirror symmetry. By using
symmetries in a model its size can be reduced by one-half or more, making this an
efficient tool for solving large problems.

The Symmetry boundary condition prescribes no penetration and vanishing shear

stresses. The boundary condition is a combination of a Dirichlet condition and a
Neumann condition:

u ⋅ n = 0,  – pI +  μ ( ∇u + ( ∇u ) T ) – 2
--- μ ( ∇ ⋅ u )I  n = 0
  3 

u ⋅ n = 0, ( – pI + μ ( ∇u + ( ∇u ) T ) )n = 0

for the compressible and incompressible formulations. The Dirichlet condition takes
precedence over the Neumann condition, and the above equations are equivalent to
the following equation for both the compressible and incompressible formulations:

u ⋅ n = 0, K – ( K ⋅ n )n = 0
K = μ ( ∇u + ( ∇u ) T )n

BOUNDARY SELECTION
For 2D axial symmetry, a boundary condition does not need to be defined for the
symmetry axis at r = 0. The software automatically provides a condition that prescribes
ur = 0 and vanishing stresses in the z direction and adds an Axial Symmetry node that
implements these conditions on the axial symmetry boundaries only.

CONSTRAINT SETTINGS
This section is displayed by clicking the Show button ( ) and selecting Advanced
Physics Options.

Open Boundary
The Open Boundary condition describes boundaries in contact with a large volume of
fluid. Fluid can both enter and leave the domain on boundaries with this type of
condition.

550 | 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 ≈ f0.

When Include gravity is selected and Use reduced pressure not selected in the interface
Physical model section, the Compensate for hydrostatic pressure approximation (named
Compensate for hydrostatic pressure for incompressible flows) check box is available and
selected by default. When it is selected, the hydrostatic pressure is automatically added
to the pressure entered in f0 user input.

No Viscous Stress
The No Viscous Stress condition specifies vanishing viscous stress on the boundary. This
condition does not provide sufficient information to fully specify the flow at the open
boundary and must at least be combined with pressure constraints at adjacent points.

The No viscous stress condition prescribes:

 μ ( ∇u + ( ∇u ) T ) – 2
--- μ ( ∇ ⋅ u )I n = 0
 3 

μ ( ∇u + ( ∇u ) T )n = 0

for the compressible and the incompressible formulations. This condition can be useful
in some situations because it does not impose any constraint on the pressure. A typical
example is a model with volume forces that give rise to pressure gradients that are hard
to prescribe in advance. To make the model numerically stable, this boundary
condition should be combined with a point constraint on the pressure.

Boundary Stress
The Boundary Stress node adds a boundary condition that represents a general class of
conditions also known as traction boundary conditions.

BOUNDARY CONDITION
The Boundary condition options for the boundary stress are General stress, Normal
stress, and Normal stress, normal flow.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 551

 General Stress
When General stress is selected, the components for the Stress F should be specified.
The total stress on the boundary is set equal to the given stress F:

 – pI +  μ ( ∇u + ( ∇u ) T ) – 2
--- μ ( ∇ ⋅ u )I  n = F
  3 

( – pI + μ ( ∇u + ( ∇u ) T ) )n = F

for the compressible and the incompressible formulations.

This boundary condition implicitly sets a constraint on the pressure that for 2D flows is

∂u n
p = 2μ ---------- – n ⋅ F (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 +  μ ( ∇u + ( ∇u ) T ) – --- μ ( ∇ ⋅ u )I  n = – f 0 ,
T 2
t⋅u = 0
3

T
n ( – pI + μ ( ∇u + ( ∇u ) T ) )n = – f 0 , t⋅u = 0

for the compressible and the incompressible formulations.

This boundary condition implicitly sets a constraint on the pressure that for 2D flows is

∂u n
p = 2μ ---------- + f 0 (7-2)
∂n

If ∂un/∂n is small, Equation 7-2 states that p ≈ f0.

When Include gravity is selected and Use reduced pressure not selected in the interface
Physical model section, the Compensate for hydrostatic pressure approximation (named
Compensate for hydrostatic pressure for incompressible flows) check box is available and
selected by default. When it is selected, the hydrostatic pressure is automatically added
to the pressure entered in f0 or phydron is added to F depending of the selected option.

552 | CHAPTER 7: FLUID FLOW INTERFACES

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 (the Destination Selection section is optional). 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).

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.

BOUNDARY SELECTION

The software usually automatically identifies the boundaries as either source boundaries or
destination boundaries, as indicated in the selection list. This works fine for cases like opposing
parallel boundaries. In other cases, right-click Periodic Flow Condition and select Manual Destination
Selection to control the destination. By default it contains the selection that COMSOL
Multiphysics identifies.

DESTINATION SELECTION
This section is available for specifying the destination boundaries, if needed, when the
Manual Destination Selection option is selected in the context menu for the Periodic Flow

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 553

 Condition node. You can only select destination boundaries from the union of all source
and destination boundaries.

FLOW CONDITION
This section is available when Incompressible flow is selected for Compressibility under
the Physical Model section for the physics interface.

The Flow Condition at the boundary is specified through a value or expression for either
·
the Pressure difference, p src – p dst , or the Mass flow, m . The mass flow option ensures
a pressure difference is achieved across the source and destination boundaries. This
pressure difference can, for example, drive the fully developed flow in a channel.

To set up a periodic boundary condition, both boundaries must be selected in the

Periodic Flow Condition node. COMSOL Multiphysics automatically assigns one
boundary as the source and the other as the destination. To manually set the
destination selection, a Destination Selection subnode is available from the context
menu (by right-clicking the parent node) or from the Physics toolbar, Attributes menu.
All destination sides must be connected.

ORIENTATION OF SOURCE
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 in the
COMSOL Multiphysics Reference Manual.

ORIENTATION OF DESTINATION
This section appears if the setting for Transform to intermediate map in the Orientation
of Source section is changed from the default value, Automatic, and Advanced Physics
Options is selected in the Show More Options dialog box. For information about the
Orientation of Destination section, see Orientation of Source and Destination in the
COMSOL Multiphysics Reference Manual.

MAPPING BETWEEN SOURCE AND DESTINATION

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
Mapping Between Source and Destination section, see Mapping Between Source and
Destination in the COMSOL Multiphysics Reference Manual.

554 | CHAPTER 7: FLUID FLOW INTERFACES

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 parts of the boundary where a source boundary lacks a corresponding destination
boundary and vice versa will get conditions from other boundary conditions under the
physics interface acting as fallback boundary conditions on the nonoverlapping parts.
By default, the Wall node is used as fallback unless another feature has been selected
for the boundary.

About Identity and Contact Pairs

Pressure Point Constraint

The Pressure Point Constraint condition can be used to specify the pressure level. If it
is not possible to specify the pressure level using a boundary condition, the pressure
level must be set in some other way, for example, by specifying a fixed pressure at a
point.

PRESSURE CONSTRAINT
The relative pressure value is set by specifying the Pressure p0. If the reference pressure
pref defined at the physics interface level is equal to zero, p0 represents the absolute
pressure.

When Include gravity is selected and Use reduced pressure not selected in the interface
Physical model section, the Compensate for hydrostatic pressure approximation (named
Compensate for hydrostatic pressure for incompressible flows) check box is available and
selected by default. When it is selected, the hydrostatic pressure is automatically added
to the pressure entered in p0 user input.

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.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 555

 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).

SOURCE STRENGTH
·
The source Mass flux, q p should be specified. A positive value results in mass being
ejected from the point into the computational domain. A negative value results in mass
being removed from the computational domain.

Point sources located on a boundary or on an edge affect the adjacent computational

domains. This has the effect, for example, that a point source located on a symmetry
plane has twice the given strength.

Mass Sources for Fluid Flow in the COMSOL Multiphysics Reference

Manual

Line Mass Source

This feature requires at least one of the following licenses: Battery Design Module,
CFD Module, Chemical Reaction Engineering Module, Corrosion Module,
Electrochemistry Module, Electrodeposition Module, Fuel Cell & Electrolyzer
Module, Microfluidics Module, Pipe Flow Module, or Subsurface Flow Module.

The Line Mass Source feature models mass flow originating from a tube region with
infinitely small radius.

For the Reacting Flow in Porous Media, Diluted Species interface, which is available
with the CFD Module, Chemical Reaction Engineering Module, or Battery Design
Module, there are two nodes, one for the fluid flow (Fluid Line Source) and one for the
species (Species Line Source).

556 | CHAPTER 7: FLUID FLOW 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 axis of symmetry
3D Edges

SOURCE STRENGTH
·
The source Mass flux, q l , should be specified. A positive value results in mass being
ejected from the line into the computational domain and a negative value means that
mass is removed from the computational domain.

Line sources located on a boundary affect the adjacent computational domains. This,
for example, has the effect that a line source located on a symmetry plane has twice the
given strength.

Mass Sources for Fluid Flow in the COMSOL Multiphysics Reference

Manual

Gravity
The Gravity global feature is automatically added when Include gravity is selected at the
interface level in the Physical Model settings. It defines the gravity forces from the
Acceleration of gravity value.

ACCELERATION OF GRAVITY
The Acceleration of gravity (SI unit m/s, default value −gconstez in 2D axial symmetry
and 3D and −gconstey in 2D) is used to define the gravity forces. It should be a global
quantity.

THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 557

 The Darcy’s Law Interface
The Darcy’s Law (dl) interface ( ), found under the Porous Media and Subsurface Flow
branch ( ) when adding a physics interface, is used to simulate fluid flow through
interstices in a porous medium. It can be used to model low-velocity flows or media
where the permeability and porosity are very small, and for which the pressure gradient
is the major driving force and the flow is mostly influenced by the frictional resistance
within the pores. Set up multiple Darcy's Law interfaces to model multiphase flows
involving more than one mobile phase. The Darcy’s Law interface can be used for
stationary and time-dependent analyses.

The main feature is the Porous Medium Properties node, which provides interfaces for
defining the fluid material and the porous matrix properties.

When this physics interface is added, the following default nodes are also added in the
Model Builder — Porous Medium, No Flow (the default boundary condition), and Initial
Values. Then, from the Physics toolbar, add other nodes that implement, for example,
boundary conditions and mass sources. You can also right-click Darcy's Law to select
physics features from the context menu.

SETTINGS
The Label is the default physics interface name.

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

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

PHYSICAL MODEL
Enter a Reference pressure level pref (SI unit: Pa). The default value is 1[atm].

GRAVITY EFFECTS
By default there are no gravity effects added to Darcy’s Law interface. Select the check
box Include gravity to activate the acceleration of gravity. When this check box is
selected a global Gravity feature node is shown in the interface model tree.

558 | CHAPTER 7: FLUID FLOW INTERFACES

Enter a value for the acceleration of gravity. The default value g_const is the
predefined standard acceleration of gravity on Earth.

This feature requires a specific license. For a detailed overview of the

functionality available in each product, visit 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.

THE DARCY’S LAW INTERFACE | 559

 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).

560 | CHAPTER 7: FLUID FLOW INTERFACES

DOMAIN

• Porous Medium • Mass Source

• Gravity • Thickness
• Cross Section • Porous Electrode Coupling
• Initial Values • Unsaturated Porous Medium

BOUNDARY, EDGE, AND POINT

The following nodes (listed in alphabetical order) are available on exterior boundaries:

• Atmosphere/Gauge • Outlet
• Electrode Surface Coupling • Pervious Layer
• Flux Discontinuity • Point Mass Source
• Fracture • Precipitation
• Hydraulic Head • Pressure
• Inlet • Pressure Head
• Interior Wall • Reaction Coefficients1
• Line Mass Source • Symmetry
• Mass Flux • Thin Barrier
• No Flow
1
This node is described for the Transport of Diluted Species Interface

The relevant physics interface condition at interior boundaries is continuity:

n ⋅ ( ρ1 u1 –ρ2 u2 ) = 0

The continuity boundary condition ensures that the pressure and mass flux are
continuous. In addition, the Pressure boundary condition is available on interior
boundaries.

THE DARCY’S LAW INTERFACE | 561

 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
• Interior Wall • Thin Barrier

For a detailed overview of the functionality available in each product, visit

https://www.comsol.com/products/specifications/

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

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

For axisymmetric components, COMSOL Multiphysics takes the axial

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

In the COMSOL Multiphysics Reference Manual see Table 2-4 for links
to common sections and Table 2-5 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Porous Medium
The Porous Medium node adds the equations for modeling flow through porous
domains. By default these are Equation 7-3 and Equation 7-4 (excluding any mass
sources).

∂
( ε ρ ) + ∇ ⋅ ( ρu ) = Q m (7-3)
∂t p

562 | CHAPTER 7: FLUID FLOW INTERFACES

 κ
u = – --- ∇p (7-4)
μ

For a steady-state problem the first term in Equation 7-3 disappears. When Gravity is
active Equation 7-4 is of the following form:

κ
u = – --- ( ∇p – ρg ) (7-5)
μ

The Porous Medium feature has two default subfeatures — the Fluid subfeature where
the fluid density ρ (SI unit: kg/m3) and dynamic viscosity μ (SI unit: Pa·s) are defined
and the Porous Matrix subfeature where the permeability κ (SI unit: m2) and porosity
εp (dimensionless) are specified.

COORDINATE SYSTEM SELECTION

Select a coordinate system from the Coordinate system list for the interpretation of
directions in anisotropic material properties. The default is the Global coordinate
system, and the list contains any additional orthonormal coordinate system (except
boundary coordinate systems) added under the Definitions node.

The subnodes inherit these coordinate system settings. In particular, the Permeability
or Hydraulic conductivity (in the Porous Matrix subnode) should be set according to
the coordinate system selected in this section.

FLOW MODEL
Define if the flow follows a linear or nonlinear pressure-velocity relationship.

• Darcian flow (default) defines a linear relationship using Equation 7-3 and
Equation 7-4.
• Non-Darcian flow defines a nonlinear relationship using Equation 7-3 and

μ
∇p = – --- u – βρ u u
κ

where the nonlinear parameter β (SI unit: 1/m) is further specified in the Porous
Matrix subfeature.

STORAGE MODEL
Equation 7-3 can also be formulated with respect to a storage term.

∂p κ
ρS ------ + ∇ ⋅ ρ – --- ( ∇p ) = Q m (7-6)
∂t μ

THE DARCY’S LAW INTERFACE | 563

 The storage coefficient S can be interpreted as the weighted compressibility of the
porous material and the fluid. Define the time dependent storage term by selecting one
of the following options from the drop-down menu:

• From density and porosity (default), uses the formulation of Equation 7-3
• Linearized storage, where the following linear equation is used to define the storage:
S = ε p χ f + ( 1 – ε p )χ p

• Poroelastic storage, where S = εpχf

• Quasistatic, where the storage term is set to zero
• User defined to directly specify the storage coefficient S

• Porous Material in the COMSOL Multiphysics Reference Manual

• About Darcian and Non-Darcian Flow in the Porous Media Flow
Module User’s Guide
• Storage Model in the Subsurface Flow Module User’s Guide

Note that some options are only available in some modules. For a detailed
overview of the functionality available in each product, visit https://
www.comsol.com/products/specifications/

Fluid
This node defines the material properties of the fluid of the Porous Medium or
Unsaturated Porous Medium parent node. The fluid can be specified as general gas or
liquid or as an ideal gas.

MODEL INPUT
This section contains fields and values that are inputs for expressions defining material
properties. If such user-defined property groups are added, the model inputs appear
here.

FLUID PROPERTIES
The available options for the Fluid type are Gas/Liquid (default) or Ideal gas. The
selection determines how the density and compressibility of the fluid are set. The latter
is only required if a poroelastic or linearized storage model has been selected in the

564 | CHAPTER 7: FLUID FLOW INTERFACES

parent Porous Medium node. For all fluid types specify the dynamic viscosity μ (SI
unit: Pa·s).

Gas/Liquid
This option specifies the Density and the Compressibility for a general gas or liquid.

Ideal Gas
For Ideal gas it uses the ideal gas law to describe the fluid. In this case, specify the
thermodynamics properties. Select a Gas constant type — Specific gas constant Rs (the
default) or Mean molar mass Mn (SI unit: J/(mol·K)). For Mean molar mass the
universal gas constant R = 8.314 J/(mol·K) is used as the built-in physical constant.
For both properties, the defaults use values From material. For User defined enter
another value or expression.

If required by a Storage Model, the Compressibility of the ideal gas is calculated as

χ f = 1 ⁄ p A with the absolute pressure pA (Pa).

Porous Matrix
This node defines the porosity and material properties of the solid matrix of the Porous
Medium or Unsaturated Porous Medium parent node.

MODEL INPUT
This section contains fields and values that are inputs for expressions defining material
properties. If such user-defined property groups are added, the model inputs appear
here.

MATRIX PROPERTIES
The default Porosity εp of the solid matrix is taken From material. In a Porous Material
node, the porosity is defined as follows:

εp = 1 –  θsi – θimfi
i i

where θsi and θimfi are the porosities of the Solid and Immobile Fluids subnodes under
the Porous Material node. See Porous Material in the COMSOL Multiphysics
Reference Manual for more information.

Select User defined to enter a value or expression for εp.

If required by a Storage model in the parent node, specify the Effective compressibility
–4
of the porous matrix. The default value is χ p = 10 1/Pa .

THE DARCY’S LAW INTERFACE | 565

 Select a Permeability model to specify the capacity of the porous material to transmit
flow. Which options are available depends on the Flow model setting in the parent node.
Note that for the Unsaturated Porous Medium parent node only the Darcian Flow
models are available.

Darcian Flow
If Darcian flow is selected in the parent Porous medium node, select between the
following options for the Permeability model:

• Select Permeability (default) to define the permeability of the porous matrix. The
default Permeability κ (SI unit: m2) uses the value From material, as defined by the
Porous material. For User defined select Isotropic to define a scalar value or Diagonal
or Symmetric to define a tensor value.
• Select Hydraulic conductivity or define a combination of fluid permeability and
dynamic viscosity. For Hydraulic conductivity K (SI unit: m/s) select Isotropic to
define a scalar value or Diagonal or Symmetric to define a tensor value. The default is
2.94·10−4 m/s.
• Select Kozeny-Carman to define the permeability from the porosity and mean particle
diameter. Enter the mean Particle diameter dp (SI unit: m), the default value is
0.5 mm.

Non-Darcian Flow
Select between the following options for the Permeability model:

• For Forchheimer, the default Permeability κ (SI unit: m2) uses the value From
material, as defined by the Porous material list. Furthermore, the dimensionless
Forchheimer parameter cF can be defined. The default value is 0.55.
• If Ergun is selected, enter the mean Particle diameter dp (default value: 0.5 mm).
• For Burke–Plummer, specify the mean Particle diameter dp (default value: 0.5 mm).
• For Klinkenberg, the default Permeability κ∞ (SI unit: m2) uses the value From
material. Enter the Klinkenberg parameter bK. Its default value is 103 Pa.

• 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

566 | CHAPTER 7: FLUID FLOW INTERFACES

 Note that some options are only available in some modules. For a detailed
overview of the functionality available in each product, visit https://
www.comsol.com/products/specifications/

RETENTION MODEL
For an Unsaturated Porous Medium select between the following options for the
retention model:

• van Genuchten, to specify the retention model using the van Genuchten relationship.
Enter the constitutive relation constants α (the default value is 1, and the SI unit is
1/m), n (default value is 2), and l (default value is 0.5). The constitutive parameter
m is equal to 1 − 1/n.
• Brooks and Corey to use the retention model according to the Brooks and Corey
relationships.
• User defined to use a different retention model. Enter user defined expressions for
the Effective saturation Se, the Liquid volume fraction θl. The default is εp (the
porosity variable). Specify the Specific moisture capacity Cm (SI unit: 1/m). The
default value is 0 (1/m). Enter an expression for the Relative permeability κr. The
default value is 1.

If there is a residual volume of liquid that cannot move through the pore network, also
enter a a value between 0 and 1 for the Residual liquid volume fraction θr. The default
value is 0.

Retention and Permeability Relationships in the Subsurface Flow Module

User’s Guide

Mass Source
The Mass Source node adds a mass source Qm, which appears on the right-hand side of
the Darcy’s Law equation (Equation 7-3).

∂ ( ρε ) + ∇ ⋅ ( ρu )
= Qm (7-7)
∂t

For the Fracture Flow interface, the mass source is applicable to the right-hand side of
Equation 4-33 in the Subsurface Flow Module User’s Guide (where it is multiplied
with the fracture thickness).

THE DARCY’S LAW INTERFACE | 567

 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
ρg

where ρ is the fluid density (SI unit: kg/m3); g denotes the acceleration of gravity
(SI unit: m/s2); and D is the elevation (SI unit: m).

INITIAL VALUES
Enter a value or expression for the initial value of the Pressure p (SI unit: Pa). The
default value is 0 Pa.

In case the Subsurface Flow Module is available, click the Pressure head button to enter
a value or expression for Hp (SI unit: m). The default is 0 m. Click the Hydraulic head
button to enter a value or expression for H (SI unit: m). The default is 0 m.

Unsaturated Porous Medium

The Unsaturated Porous Medium node adds the Richards’ equation (Equation 7-8) for
flow in variably saturated porous media.

Cm ∂p κr κ
ρ  -------- + S e S p ------ + ∇ ⋅ ρ  – -------- ( ∇p + ρ g ∇D ) = Q m (7-8)
 ρg  ∂t  μ 

The Unsaturated Porous Medium feature has two default subfeatures — the Fluid
subfeature where the fluid density ρ (SI unit: kg/m3) and viscosity μ (SI unit: Pa·s) are
defined and the Porous Matrix subfeature where the permeability κ (SI unit: m2) and
porosity εp (dimensionless) are specified as well as the retention model.

568 | CHAPTER 7: FLUID FLOW INTERFACES

COORDINATE SYSTEM SELECTION
Select a coordinate system from the Coordinate system list for the interpretation of
directions in anisotropic material properties. The default is the Global coordinate
system, and the list contains any additional orthonormal coordinate system (except
boundary coordinate systems) added under the Definitions node.

The subnodes inherit these coordinate system settings. In particular, the Permeability
or Hydraulic conductivity (in the Porous Matrix subnode) should be set according to
the coordinate system selected in this section.

STORAGE MODEL
With this option, define the first term in Equation 7-8. Therefore, choose from a
drop-down menu one of the following formulations:

• From retention model

• Linearized storage (default)
• From liquid content
• User defined

If From retention model is chosen, the first term of Equation 7-8 accounts only for the
specific moisture capacity Cm which is defined by the Retention Model in the Porous
Matrix subnode:

C m ∂p
-------- .
g ∂t

For the option Linearized storage the storage coefficient Sp in Equation 7-8 is defined
as

S p = ε p χ f + ( 1 – ε p )χ p .

From liquid content enforces the first term of Equation 7-8 to be defined in terms of
liquid volume fraction as

∂( ρθ l )
----------------
∂t

and the User defined option allows to define the storage coefficient Sp in Equation 7-8
directly.

THE DARCY’S LAW INTERFACE | 569

 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.

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). The
Acceleration of gravity is taken From physics interface by default but could be overridden
when User defined is selected.

When the check box Include gravity is not selected in the Darcy’s Law interface
Settings, the elevation D is set equal to zero.

Select the check box Specify reference position to define a reference position for the
gravity calculation.

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.

570 | CHAPTER 7: FLUID FLOW INTERFACES

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 (the 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.

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.

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 DARCY’S LAW INTERFACE | 571

 The flow is proportional to the Molar mass (kg/mol) of the reacting species, the current
densities and the stoichiometric coefficients according to Faraday’s law as defined by
summation over the Reaction Coefficient subnodes.

SPECIES
Based on the number of species required for the model, use the Add ( ) and
Delete ) buttons under the table to add or remove Species. Then enter a value for
the Molar mass (kg/mol) in the applicable rows for each species.

The setting in the table will determine the number of available field for entering the
stoichiometric coefficients of the Reaction Coefficient subnodes.

Pressure
Use the Pressure node to specify the pressure on a boundary. In many cases the
distribution of pressure is known, giving a Dirichlet condition p = p0 where p0 is a
known pressure given as a number, a distribution, or an expression involving time, t,
for example.

PRESSURE
Enter a value or expression for the Pressure p0 (SI unit: Pa). Enter a relative pressure
value in p0 (SI unit: Pa).

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.

As an attribute to the Fracture boundary condition or as boundary condition to The

Fracture Flow Interface (which are available in the Subsurface Flow Module and the
Porous Media Flow Module), the pressure can also be specified on edges (in 3D) or
points (in 2D) surrounding the fracture domain. In other cases, pressure constraints
on edges or points 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

572 | CHAPTER 7: FLUID FLOW INTERFACES

the pumping rate or from measurements. With this boundary condition, positive
values correspond to flow into the model domain:

κ
n ⋅ ρ --- ( ∇p + ρ g ∇D ) = N 0
μ

where N0 is a value or expression for the specified inward (or outward) Darcy flux. D
is the elevation head which is set to zero for other than Subsurface Flow Module
applications.

MASS FLUX
Enter a value or expression for the Inward mass flux N0. A positive value of N0
represents an inward mass flux whereas a negative value represents an outward mass
flux. The units are based on the geometric entity: Boundaries: (SI unit: kg/(m2·s)).

Line Mass Source

The Line Mass Source node adds mass flow originating from a tube of infinitely small
radius.

SELECTION
The Line Mass Source feature is available for all dimensions, but the applicable selection
differs between the dimensions.

MODEL DIMENSION APPLICABLE GEOMETRICAL ENTITY

2D Points
2D Axisymmetry Points not on the symmetry axis
3D Edges

LINE MASS SOURCE

Enter a value or expression for the source strength, N0 (SI unit: kg/(m·s)). A positive
value results in mass injection from the line into the computational domain, and a
negative value means that the mass is removed from the computational domain.

Line sources located on a boundary affect the adjacent computational domains. This
effect makes the physical strength of a line source located in a symmetry plane twice
the given strength.

THE DARCY’S LAW INTERFACE | 573

 Fracture Flow
The equivalent feature available for fracture flow is the Mass Source attribute of the
Fracture boundary condition and the Mass Source point feature of the Fracture Flow
Interface, both available in 3D only.

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:

VELOCITY
Enter a value or expression for the Normal inflow velocity U0 (SI unit: m/s). A positive
value of U0 represents an inflow velocity. A negative value represents an outflow
velocity. The inlet velocity boundary condition is implemented as;

κ
n ⋅ ρ --- ( ∇p + ρ g ∇D ) = ρU 0
μ

where U0 is a value or expression for the specified inward (or outward) Darcy velocity.
A positive value of the velocity U0 corresponds to flow into the model domain whereas
a negative value represents an outflow. D is the elevation head which is set to zero for
other than Subsurface Flow Module applications.

574 | CHAPTER 7: FLUID FLOW INTERFACES

PRESSURE
Use the Pressure option to specify the inlet pressure on a boundary. In many cases the
distribution of pressure is known, giving a Dirichlet condition p = p0 where p0 is a
known pressure given as a number, a distribution, or an expression involving time, t,
for example. Enter a value or expression for the Pressure p0 (SI unit: Pa).

MASS FLOW
If you select Mass flow as the inlet condition, specify the total Mass flow rate M0 (SI
unit: kg/s), or the Pointwise mass flux N0 (SI unit: kg/(m2·s)).

With Mass flow rate boundary condition, positive values correspond to flow into the
model domain:

–  ρ ( u ⋅ n ) dS = M0
∂Ω

where M0 is a value or expression for the specified inward (or outward) Darcy flux.

Pointwise mass flux boundary condition, positive values correspond to flow into the
model domain:

κ
n ⋅ ρ --- ( ∇p + ρ g ∇D ) = N 0
μ

where N0 is a value or expression for the specified inward (or outward) Darcy flux.

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

Symmetry
The Symmetry node describes a symmetry boundary. The following condition
implements the symmetry condition on an axis or a flow divide:

κ
n ⋅ --- ∇p = 0
μ

κ
n ⋅ --- ( ∇p + ρ g ∇D ) = 0
μ

THE DARCY’S LAW INTERFACE | 575

 For axisymmetric components, COMSOL Multiphysics takes the axial symmetry
boundaries (at r = 0) into account and automatically adds an Axial Symmetry node that
is valid on the axial symmetry boundaries only.

No Flow
The No Flow node is the default boundary condition stating that there is no flow across
impermeable boundaries. The mathematical formulation is:

κ
n ⋅ ρ --- ( ∇p + ρ g ∇D ) = 0
μ

where n is the vector normal to the boundary. D is the elevation head which is set to
zero for any other than Subsurface Flow Module applications.

Flux Discontinuity
Use the Flux Discontinuity node to specify a mass flux discontinuity through an interior
boundary. The condition is represented by the following equation:

– n ⋅ ( ρu 1 – ρ u 2 ) = N 0

In this equation, n is the vector normal (perpendicular) to the interior boundary, ρ is

the fluid density, u1 and u2 are the Darcy velocities in the adjacent domains (as defined
in Equation 7-9) and N0 is a specified value or expression for the flux discontinuity.

κ
u = – --- ∇p (7-9)
μ

For this boundary condition, a positive value of N0 corresponds to a flow discontinuity

in the opposite direction to the normal vector of the interior boundary.

MASS FLUX
Enter a value or expression for the Inward mass flux N0 (SI unit: kg/(m2·s)). A positive
value of N0 represents a mass flux discontinuity in the opposite direction to the normal
vector of the interior boundary.

576 | CHAPTER 7: FLUID FLOW INTERFACES

Outlet
The Outlet node adds a boundary condition for the outflow (or inflow) perpendicular
(normal) to the boundary. It has different options that can be used to specify inlet
condition on a boundary, as follows:

VELOCITY
Enter a value or expression for the Normal outflow velocity U0 (SI unit: m/s). A positive
value of U0 represents an outflow velocity whereas a negative value represents an
inflow velocity.

κ
– n ⋅ ρ --- ∇p = ρU 0
μ

where U0 is a specified value or expression for the outward (or inward) Darcy velocity.

PRESSURE
Similar to the inlet Pressure option, the outlet pressure on a boundary can be specified.
Enter a value or expression for the Pressure p0 (SI unit: Pa).

DISCHARGE
Enter a value or expression for the discharge QD to specify the volumetric flow rate
through the boundary. The mass flux ρu is related to the discharge as follows:

 ρu ⋅ ds = ρQ D . (7-10)
∂Ω

The mean normal outflow velocity at the boundary can then be calculated as Uout =
QD/A, where A is the cross sectional area of the boundary.

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.

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

THE DARCY’S LAW INTERFACE | 577

 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.

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.

WALL
Enter a value or expression for the Thickness db (SI unit: m, the default is 0.1 m) and
for the Permeability κb (SI unit: m2). The default Permeability κb uses the value From
material. For User defined select Isotropic to define a scalar value or Diagonal, Symmetric,
or Full to define a tensor value and enter another value or expression in the field or
matrix.

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).

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.

578 | CHAPTER 7: FLUID FLOW INTERFACES

HYDRAULIC HEAD
Enter a value or expression for the Hydraulic head H0 (SI unit: m). The default is 0 m.

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

Atmosphere/Gauge
The Atmosphere/Gauge node specifies an atmospheric pressure or gauges the pressure
to the atmospheric value. This means that the total hydraulic potential reduces to the
gravitational pressure at the free surface. At a free surface, such as a spring or a seepage
face, the pressure is atmospheric. If the pressures in the model is gauged to the
atmospheric value (p = 0), the total hydraulic potential reduces to the gravitational
potential at the free surface — for example, the height of the free surface multiplied by
the fluid weight, or ρf gD. This boundary condition sets the pressure at the boundary
to zero and p = 0.

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 Pervious Layer node provides a boundary condition that describes a mass flux
through a semi-pervious layer connected to an external fluid source at different
pressure, pressure head, or hydraulic head. The model domain might connect to a
larger body of water through the semi-pervious layer. This condition is represented
with the following boundary condition:

κ ( pb – p )
n ⋅ ρ --- ( ∇p + ρ g ∇D ) = ρR b -------------------- + ( D b – D ) (7-11)
μ ρg

In this equation, pb (SI unit: Pa) and Db (SI unit: m) are the pressure and the elevation
of the distant fluid source, respectively, and Rb (SI unit: 1/s) is the conductance of
materials between the source and the model domain (conductance to flow in the
semi-pervious layer adjacent to the boundary). Typically Rb = K'/B', where K' is the
hydraulic conductivity (SI unit: m/s) of the layer and B' (SI unit: m) is its thickness.

THE DARCY’S LAW INTERFACE | 579

 Using logical relationships, it is possible to activate these expressions at different times
or under various flow conditions.

When the pressure head Hp is specified instead of the pressure, the boundary condition
is the following:

n ⋅ ρK∇ ( H p + D ) = ρR b [ ( H pb – H p ) + ( D b – D ) ] (7-12)

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 ⋅ ρK∇H = ρR b [ H b – H ] (7-13)

Hb is the hydraulic head (SI unit: m) at the edge of the layer.

K in Equation 7-12 and Equation 7-13 is the hydraulic conductivity.

At a free surface, such as a water table or seepage face, the pressure is atmospheric (here
taken to be zero), so the total hydraulic potential equals gravitational potential, which
is defined on D.

Gravity effects are not active by default. Select the check box Include
gravity to activate the acceleration of gravity. Setting the elevation D to
zero also turns off gravity effects.

PERVIOUS LAYER
Specify the material properties whether to specify an external pressure, pressure head,
or hydraulic head.

Select an External variable to specify — Pressure and elevation to specify the external
pressure, Pressure head and elevation to specify the external pressure head, or Hydraulic
head. For all selections, enter a value for the Conductance Rb (SI unit: 1/s).

• For Pressure and elevation enter an External pressure pb (SI unit: Pa) and External
elevation Db (SI unit: m).
• For Pressure head and elevation enter an External pressure head Hpb (SI unit: m), Hpb
(SI unit: m) and External elevation Db (SI unit: m).
• For Hydraulic head enter the Hydraulic head Hb (SI unit: m).

580 | CHAPTER 7: FLUID FLOW INTERFACES

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
Use the Fracture node to model flow along a boundaries representing fractures within
a porous medium. By default, it adds the tangential form of the continuity equation
and of Darcy’s Law.

∂
d f ----- ( ε p ρ ) + ∇ T ⋅ ( d f ρu ) = d f Q m (7-14)
∂t

κ
u = – --- ∇Tp (7-15)
μ

The Fracture feature has two default subfeatures — the Fluid (Fracture) subfeature
where the fluid density ρ (SI unit: kg/m3) and dynamic viscosity μ (SI unit: Pa·s) are
defined and the Fracture Material subfeature where the permeability κ (SI unit: m2)
and porosity εp (dimensionless) are specified.

COORDINATE SYSTEM SELECTION

Select a coordinate system from the Coordinate system list for the interpretation of
directions in anisotropic material properties. The default is the Global coordinate
system, and the list contains any additional orthonormal coordinate system (except
boundary coordinate systems) added under the Definitions node.

The subnodes inherit these coordinate system settings. In particular, the Permeability
or Hydraulic conductivity (in the Fracture Material subnode) should be set according to
the coordinate system selected in this section.

THE DARCY’S LAW INTERFACE | 581

 APERTURE
Enter a value for the Fracture thickness df.

FLOW MODEL
Define if the flow follows a linear or nonlinear pressure-velocity relationship.

• Darcian flow (default) defines a linear relationship using Equation 7-14 and
Equation 7-15.
• Non-Darcian flow defines a nonlinear relationship using Equation 7-14 and the
pressure-velocity relationship

μ
∇Tp = – --- u – βρ u u
κ

where the nonlinear parameter β (SI unit: 1/m) is further specified in the Fracture
Material subfeature.

STORAGE MODEL
Equation 7-14 can also be formulated with respect to a storage term.

∂p κ
ρS ------ + ∇ ⋅ ρ – --- ( ∇p ) = Q m
∂t μ

The storage coefficient S can be interpreted as the weighted compressibility of the

porous material and the fluid. Define the time dependent storage term by selecting one
of the following options from the drop-down menu:

• From density and porosity (default), uses the formulation of Equation 7-14
• Linearized storage, where the following linear equation is used to define the storage:
S = ε p χ f + ( 1 – ε p )χ p

• User defined to directly specify the storage coefficient S

• About Darcian and Non-Darcian Flow in the Porous Media Flow

Module User’s Guide
• Storage Model in the Subsurface Flow Module User’s Guide

582 | CHAPTER 7: FLUID FLOW INTERFACES

FRACTURE MODEL
Choose between two options to model fractures that have different characteristics.

• Highly conductive fracture represents a fracture filled with a highly permeable

material.
• Thin conducting barrier represents a fracture that is filled with a low permeable
material and therefore acts as a barrier for the flow which adds a jump in the pressure
across the boundary:

( p d,u – p u,d ) κ b
– n u,d ⋅ ( ρu ) u,d = ρ ------------------------------- ------
db μ

The barrier thickness db and permeability κb are defined in the Fracture Material
subnode.
In addition, either on the upside, downside, or on both sides a highly conductive
fracture material is present and Equation 7-14 and Equation 7-15 are solved for the
highly conductive side. Further specifications are done in the Fracture Material
subnode.

Note that the option to specify the Fracture Model is only available for the
Fracture feature within the Darcy’s Law interface.

For the Fracture boundary node several subnodes are available from the context menu
(right-click the parent node) or from the Physics toolbar, Attributes menu. As they are
almost identical to the boundary conditions of the Fracture Flow interface, see
Domain, Boundary, Edge, Point, and Pair Nodes for the Fracture Flow Interface in
the Subsurface Flow User’s Guide for further description. Note that Precipitation is
only available for the Fracture Flow 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/.

Flow in a Fractured Reservoir: Application Library path

Subsurface_Flow_Module/Fluid_Flow/fractured_reservoir_flow

THE DARCY’S LAW INTERFACE | 583

 Fluid (Fracture)
This node defines the material properties of the fluid of the Fracture parent node. The
fluid can be specified as general gas or liquid or as an ideal gas.

MODEL INPUT
This section contains fields and values that are inputs for expressions defining material
properties. If such user-defined property groups are added, the model inputs appear
here.

FLUID PROPERTIES
The available options for the Fluid type are Gas/Liquid (default) or Ideal gas. The
selection determines how the density and compressibility of the fluid are set. The latter
is only required if a linearized storage model has been selected in the parent Fracture
node. For all fluid types specify the dynamic viscosity μ (SI unit: Pa·s).

Gas/Liquid
This option specifies the Density and the Compressibility for a general gas or liquid.

Ideal Gas
For Ideal gas it uses the ideal gas law to describe the fluid. In this case, specify the
thermodynamics properties. Select a Gas constant type — Specific gas constant Rs (the
default) or Mean molar mass Mn (SI unit: J/(mol·K)). For Mean molar mass the
universal gas constant R = 8.314 J/(mol·K) is used as the built-in physical constant.
For both properties, the defaults use values From material. For User defined enter
another value or expression.

If required by a Storage Model, the Compressibility of the ideal gas is calculated as

χ f = 1 ⁄ p A with the absolute pressure pA (Pa).

If Hydraulic conductivity is selected as the Permeability model (see the

Fracture Material section), dynamic viscosity is not available. The
hydraulic conductivity is defined using a combination of fluid and fracture
material properties and replaces the need of defining the dynamic
viscosity.

Fracture Material
This node defines the porosity and material properties of the solid matrix of the
Fracture parent node.

584 | CHAPTER 7: FLUID FLOW INTERFACES

MODEL INPUT
This section contains fields and values that are inputs for expressions defining material
properties. If such user-defined property groups are added, the model inputs appear
here.

BARRIER PROPERTIES
This section appears if the Thin conducting barrier option for the Fracture model is
chosen in the parent Fracture feature.

Enter the values for the barrier thickness db and permeability κb.

Note that the Thin Conductive barrier option is only available for the Fracture feature
within the Darcy’s Law interface.

FRACTURE MATERIAL PROPERTIES

If the Thin conducting barrier option for the Fracture model is chosen in the parent
Fracture feature you can specify the Conductive layer position here. Choose between
Both sides, Upside, and Downside. A sketch above shows the position of conductive
layers and barrier within the fracture.

The Porosity εp of the fracture material is taken From material by default. Select User
defined to enter a value or expression for εp.

If required by a Storage model in the parent node, specify the Effective compressibility
–4
of the porous matrix. The default value is χ p = 10 1/Pa .

Select a Permeability model to specify the capacity of the fracture material to transmit
flow. Which options are available depends on the Flow model setting in the parent node.

• Select Permeability (default) to define the permeability of the fracture material.

• Select Hydraulic conductivity or define a combination of fluid permeability and
dynamic viscosity. For Hydraulic conductivity K (SI unit: m/s) select Isotropic to
define a scalar value or Diagonal or Symmetric to define a tensor value. The default is
2.94·10−4 m/s.
• Select Cubic law to define the permeability from the fracture thickness specified in
the parent node and the roughness factor ff.

THE DARCY’S LAW INTERFACE | 585

 If the Non-Darcian Flow Model is selected in the parent Fracture feature enter a value
for the Inertial resistance coefficient β.

• 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

586 | CHAPTER 7: FLUID FLOW INTERFACES

The Free and Porous Media Flow
Interface
The Free and Porous Media Flow (fp) interface ( ) is found under the Porous Media
and Subsurface Flow branch ( ) when adding a physics interface. It is used to
compute fluid velocity and pressure fields of single-phase flow where free flow is
connected to porous media. The Free and Porous Media Flow interface is used over at
least two different domains: a free channel and a porous medium. The physics interface
is well suited for transitions between slow flow in porous media, governed by the
Brinkman equations, and fast flow in channels described by the Navier–Stokes
equations. Fluids with varying density can be included at Mach numbers below 0.3.
Also the viscosity of a fluid can vary, for example, to describe non-Newtonian fluids.
The physics interface can be used for stationary and time-dependent analyses.

When this physics interface is added, the following default nodes are also added in the
Model Builder — Fluid Properties, Wall, and Initial Values. Then, from the Physics
toolbar, add a Porous Medium node to be used on the domain selection corresponding
to the porous media, or add other nodes that implement, for example, boundary
conditions and volume forces. You can also right-click Free and Porous Media Flow to
select physics features from the context menu.

SETTINGS
The Label is the default physics interface name.

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

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

PHYSICAL MODEL

Compressibility
By default the physics interface uses the Incompressible flow formulation of the Navier–
Stokes and Brinkman equations to model constant density flow. If required, select
Weakly compressible flow from the Compressibility list, to account for small variations in

THE FREE AND POROUS MEDIA FLOW INTERFACE | 587

 the density, which are only dependent on the temperature (nonisothermal flow) or
Compressible flow (Ma<0.3) for fully compressible flow. However, for the flow modeled
with this physics interface, the Mach number must be below 0.3.

Swirl Flow
For 2D axisymmetric components, select the Swirl flow check box to include the swirl
velocity component, that is the velocity component u ϕ in the azimuthal direction.
While u ϕ can be nonzero, there can be no gradients in the ϕ direction. Note that this
feature is only available for specific modules. Visit https://www.comsol.com/
products/specifications/ for a detailed overview.

Neglect Inertial Term

Select the Neglect inertial term (Stokes flow) check box if the inertial forces are small
compared to the viscous forces.

Enable porous media domains

The Enable porous media domains check box is selected by default to solve the
Brinkman equations in porous domains. If it is unchecked, the Porous Medium node is
no longer available in this interface.

Include Gravity
Gravity is not included by default. Select the Include gravity check box to activate the
acceleration of gravity. This automatically adds a global Gravity feature node to the
interface model tree, and the buoyancy force is included in the Equations.

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

Porous Treatment of No Slip Condition

Choose how the No Slip condition on internal boundaries should be treated. The
options are Standard no slip formulation (default) and Porous slip. The latter option
provides a unified treatment when the porous matrix is fully resolved as well as when
it is under-resolved ensuring a smooth transition between regions with different
resolutions; see No Slip under Wall in the The Laminar Flow and Creeping Flow
Interfaces section.

Reference Pressure Level

Enter a Reference pressure level pref (SI unit: Pa). The default value is 1[atm].

588 | CHAPTER 7: FLUID FLOW INTERFACES

Reference Temperature
Enter a Reference temperature Tref (SI unit: K). The default value is 293.15[K].

Reference Position
If Include gravity is selected, a Reference position rref (SI unit: m) can be specified which
is then used for the calculation of the hydrostatic pressure.

TURBULENCE
Turbulent flow can be simulated by changing the Turbulence model type to RANS
(Reynolds-Averaged Navier–Stokes) or Large Eddy Simulation (which is only available
in 3D). If turbulent flow is activated, you can choose from different Turbulence models
and options for Wall treatment. For a description of the different turbulence models,
wall treatment options, and turbulence model parameters see Theory for the
Turbulent Flow Interfaces in the CFD Module User’s Guide.

DEPENDENT VARIABLES
The following dependent variables (fields) are defined for this physics interface — the
Velocity field u (SI unit: m/s) and its components, and the Pressure p (SI unit: Pa).

• Domain, Boundary, Point, and Pair Nodes for the Free and Porous
Media Flow Interface
• Theory for the Free and Porous Media Flow Interface

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

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

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

THE FREE AND POROUS MEDIA FLOW INTERFACE | 589

 • Electrode Surface Coupling • Porous Medium
• Fluid Properties • Mass Source
• Gravity • Volume Force
• Initial Values • Wall

Note that some features are only available with certain COMSOL products (see
https://www.comsol.com/products/specifications/).

See the Transport of Diluted Species interface for Porous Electrode

Coupling and Reaction Coefficients.

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.

590 | CHAPTER 7: FLUID FLOW INTERFACES

The default Density ρ (SI unit: kg/m3) uses values From material based on the Fluid
material selection. For User defined enter another value or expression. The default is
0 kg/m3.

The Dynamic viscosity μ (SI unit: Pa·s) uses values From material based on the Fluid
material selection. For User defined enter another value or expression. The default is
0 Pa·s.

Porous Medium

The Porous Medium node adds the Brinkman equations (excluding any mass sources)
to the interface. It has two default subfeatures — the Fluid subfeature where the fluid
density ρ(SI unit: kg/m3) and dynamic viscosity μ (SI unit: Pa·s) are defined and the
Porous Matrix subfeature where the permeability κ (SI unit: m2) and porosity εp
(dimensionless) are specified.

FLOW MODEL
Define if the flow follows a linear or nonlinear pressure-velocity relationship.

• Darcian flow (default) defines a linear relationship characteristic for low Reynolds
number laminar flows.
• Non-Darcian flow defines a nonlinear relationship due to inertial or turbulence
effects.

POROUS MEDIUM TURBULENCE MODEL

Defines a model which complements the basic turbulence model and accounts for the
influence of the porous matrix on turbulent flow in Porous Media.

• Default and Nakayama-Kuwahara specify Coefficient of subgrid turbulence generation

by porous matrix Cstpm which by default is set to 0.212.
• Pedras-de Lemos asks to specify Choice of the Pedras-de Lemos model coefficient. When
User defined is chosen, specify Coefficient of subgrid turbulence generation by porous
matrix Cstpm with default value 0.212. Choosing Original results in
C stpm = 0.28 ⋅ ε p , while choosing Recalibrated results in C stpm = 0.18 .

Fluid
This node defines the material properties of the fluid of the Porous Medium parent
node.

THE FREE AND POROUS MEDIA FLOW INTERFACE | 591

 MODEL INPUT
This section contains fields and values that are inputs for expressions defining material
properties. If such user-defined property groups are added, the model inputs appear
here.

FLUID PROPERTIES
Specify the Density ρ and the Dynamic viscosity μ (SI unit: Pa·s) of the fluid. The
defaults use values From material, for User defined enter a value or expression.

The dynamic viscosity describes the relationship between the shear stresses and the
shear rate in a fluid. Intuitively, water and air have a low viscosity, and substances often
described as thick, such as oil, have a higher viscosity.

Porous Matrix
This node defines the porosity and material properties of the solid matrix of the Porous
Medium parent node.

MODEL INPUT
This section contains fields and values that are inputs for expressions defining material
properties. If such user-defined property groups are added, the model inputs appear
here.

MATRIX PROPERTIES
The Porosity εp (a dimensionless number between 0 and 1) uses by default the value
From material. For User defined the default value is 1 which is equivalent to free flow.

Select a Permeability model to specify the capacity of the porous material to transmit
flow. Depending on the Flow model selection in the parent Porous Medium feature node
you can choose between the following options:

• Permeability (the default) to directly enter the permeability of the porous matrix or
Kozeny-Carman to define the permeability from the porosity and mean Particle
diameter for Darcian flow or
• Forchheimer or Ergun for Non-Darcian flow.

Note that some of these options are only available for certain modules. For a detailed
overview of the functionality available in each product, visit https://
www.comsol.com/products/specifications/.

592 | CHAPTER 7: FLUID FLOW INTERFACES

The default Permeability κ (SI unit: m2) uses the value From material, as defined by the
Porous material list. For User defined select Isotropic to define a scalar value or Diagonal
or Symmetric to define a tensor value.

For Kozeny-Carman, enter the mean Particle diameter dp (SI unit: m), the default value
is 0.5 mm.

In case a Non-Darcian flow model is chosen in the parent node, Forchheimer is the
default selection for the Permeability model. For Forchheimer, the default Permeability
κ (SI unit: m2) uses the value From material. Furthermore, the dimensionless
Forchheimer parameter cF can be defined. The default value is 0.55.

If Ergun is selected, enter the mean Particle diameter dp (default value: 0.5 mm). The
permeability κ is then calculated using Equation 2-4 in the Porous Media Flow
Module User’s Guide.

• About Darcian and Non-Darcian Flow in the Porous Media Flow

Module User’s Guide
• Permeability Models in the Porous Media Flow Module User’s Guide

Mass Source
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 a Fluid Properties or Porous
Medium node is active on the domain. It then acts on each fluid element in the
specified domains.

THE FREE AND POROUS MEDIA FLOW INTERFACE | 593

 VOLUME FORCE
Enter the components of the Volume force F (SI unit: N/m3).

Porous Electrode Coupling

Use the Porous Electrode Coupling node to define a mass source based on the volumetric
current densities of one or multiple Porous Electrode Reaction nodes in an
Electrochemistry interface.

The source (or sink) is proportional to the Molar mass (kg/mol) of the reacting species,
the current densities and the stoichiometric coefficients according to Faraday’s law as
defined by summation over the Reaction Coefficient subnodes.

SPECIES
Based on the number of species required for the model, use the Add ( ) and
Delete ) buttons under the table to add or remove Species. Then enter a value for
the Molar mass (kg/mol) in the applicable rows for each species.

The setting in the table will determine the number of available fields for entering the
stoichiometric coefficients of the Reaction Coefficient subnodes.

Initial Values
The Initial Values node adds initial values for the velocity field and the pressure that can
serve as an initial condition for a transient simulation or as an initial guess for a
nonlinear solver.

INITIAL VALUES
Enter initial values or expressions for the Velocity field u (SI unit: m/s) and for the
Pressure p (SI unit: Pa). The default values are 0 m/s and 0 Pa, respectively.

Gravity
The Gravity global feature is automatically added when Include gravity is selected at the
interface level in the Physical Model settings. It defines the gravity forces from the
Acceleration of gravity value. When a turbulence model that solves for the turbulent
kinetic energy, k, is used, the option Include buoyancy-induced turbulence is available.
When selected, the Buoyancy contribution is by default set to Automatic from
multiphysics. Contributions are only obtained from multiphysics couplings that
support buoyancy-induced turbulence, such as Nonisothermal Flow. If the Buoyancy

594 | CHAPTER 7: FLUID FLOW INTERFACES

contribution is switched to User defined, a text field for the Turbulent Schmidt number
appears. See also Theory for Buoyancy-Induced Turbulence in the CFD Module
User’s Guide.

This feature requires a specific license. For a detailed overview of the functionality
available in each product visit https://www.comsol.com/products/specifications/.

ACCELERATION OF GRAVITY
The Acceleration of gravity (SI unit m/s, default value −gconstez in 2D axial symmetry
and 3D and −gconstey in 2D) is used to define the gravity forces. It should be a global
quantity.

Electrode-Electrolyte Interface Coupling

Use the Electrode-Electrolyte Interface Coupling node to define a combined wall and
inflow/outflow boundary condition based on current densities of one or multiple
Electrode Reaction nodes in an Electrochemistry interface.

The flow is proportional to the Molar mass (kg/mol) of the reacting species, the current
densities and the stoichiometric coefficients according to Faraday’s law as defined by
summation over the Reaction Coefficient subnodes.

TANGENTIAL VELOCITY CONDITION

For information about this section, see the Wall node. No slip is the default, but Slip
may in some cases be a more applicable, for instance if a gas diffusion electrode is
modeled as a boundary condition.

SPECIES
Based on the number of species required for the model, use the Add ( ) and
Delete ) buttons under the table to add or remove Species. Then enter a value for
the Molar mass (kg/mol) in the applicable rows for each species.

The setting in the table will determine the number of available field for entering the
stoichiometric coefficients of the Reaction Coefficient subnodes.

Wall
The Wall node includes a set of boundary conditions describing fluid-flow conditions
at stationary, moving, and leaking walls.

THE FREE AND POROUS MEDIA FLOW INTERFACE | 595

 BOUNDARY CONDITION
Select a Boundary condition for the wall.

• No Slip1 • Leaking Wall

• Slip

No Slip
No slip is the default boundary condition for a stationary solid wall for laminar flow
(and SST, Low Re k-ε, Algebraic yPlus, L-VEL, and Spalart-Allmaras turbulence
models). The condition prescribes u = 0; that is, the fluid at the wall is not moving.

Slip
The Slip option prescribes a no-penetration condition, u·n = 0. It is implicitly assumed
that there are no viscous effects at the slip wall and hence, no boundary layer develops.
From a modeling point of view, this can be a reasonable approximation if the main
effect of the wall is to prevent fluid from leaving the domain.

Leaking Wall
This boundary condition may be used to simulate a wall where fluid is leaking into or
leaving the domain with the velocity u = ul through a perforated wall. The
components of the Fluid velocity ul on the leaking wall should be specified.

CONSTRAINT SETTINGS
This section is displayed by clicking the Show button ( ) and selecting Advanced
Physics Options.

• The Moving Mesh Interface in the COMSOL Multiphysics Reference

Manual

596 | 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 Porous Medium feature, which adds the Brinkman equations and
provides interfaces for defining the fluid material and the porous matrix.

When this physics interface is added, the following default nodes are also added in the
Model Builder — Porous Medium, Wall (the default boundary type, using No slip as the
default boundary condition), and Initial Values. Then, from the Physics toolbar, add
other nodes that implement, for example, boundary conditions and volume forces.
You can also right-click Brinkman Equations to select physics features from the context
menu.

The boundary conditions are essentially the same as for the Laminar Flow interface.
Differences exist for the following boundary types: Outlet, Symmetry, Open
Boundary, and Boundary Stress where the viscous part of the stress is divided by the
porosity to appear as

1-  T 2 
---- μ ( ∇u + ( ∇u ) ) – --- μ ( ∇ ⋅ u )I 
ε p  3 

In the COMSOL Multiphysics Reference Manual see Table 2-4 for links to common
sections such as Discretization, Consistent Stabilization, Inconsistent Stabilization, and
Advanced Settings, all accessed by clicking the Show button ( ) and choosing the
applicable option. You can also search for information: press F1 to open the Help
window or Ctrl+F1 to open the Documentation window.

SETTINGS
The Label is the default physics interface name.

THE BRINKMAN EQUATIONS INTERFACE | 597

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

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

PHYSICAL MODEL
This node specifies the properties of the Brinkman Equations interface, which describe
the overall type of fluid flow model.

Compressibility
By default the physics interface uses the Incompressible flow formulation of the
Brinkman equations to model constant density flow. Alternatively, from the
Compressibility list select Weakly compressible flow, which should be used when the
pressure dependency of the density can be neglected, or Compressible flow (Ma<0.3) to
solve for the full compressible flow of which, however, the Mach number must be
below 0.3.

Swirl Flow
For 2D axisymmetric models, select the Swirl flow check box to include the swirl
velocity component, that is the velocity component u ϕ in the azimuthal direction.
While u ϕ can be nonzero, there can be no gradients in the ϕ direction.

Note that this feature is only available for specific modules. See https://
www.comsol.com/products/specifications/ for a detailed overview.

Neglect Inertial Term (Stokes–Brinkman Flow)

The Neglect inertial term (Stokes–Brinkman) check box is selected by default to model
flow at low Reynolds numbers for which the inertial term can be neglected. This results
in the linear Stokes–Brinkman equations.

Include Gravity
Gravity is not included by default. Select the Include gravity check box to activate the
acceleration of gravity. This automatically adds a global Gravity feature node to the
interface model tree, and the buoyancy force is included in the Equations.

Also, when the Include gravity check box is selected, the Use reduced pressure option
changes the pressure formulation from using the total pressure (default) to using the
reduced pressure. This option is suitable for configurations where the density changes

598 | CHAPTER 7: FLUID FLOW INTERFACES

are very small; otherwise, the default formulation can be used. For more information,
see Gravity.

Porous Treatment of No Slip Condition

Choose how the No Slip condition on Wall boundaries and Interior Wall boundaries
adjacent to Porous Medium should be treated. The options are Standard no slip
formulation (default) and Porous slip. The latter option provides a unified treatment
when the porous matrix is fully resolved as well as when it is under-resolved ensuring
a smooth transition between regions with different resolutions; see No Slip under Wall
in the The Laminar Flow and Creeping Flow Interfaces section.

Reference Pressure Level

Enter a Reference pressure level pref (SI unit: Pa). The default value is 1[atm].

Reference Temperature Level

Enter a Reference temperature level Tref (SI unit: K). The default value is 293.15[K].

Reference Position
If Include gravity is selected, a Reference position rref (SI unit: m) can be specified which
is then used for the calculation of the hydrostatic pressure.

TURBULENCE
Turbulent flow can be simulated by changing the Turbulence model type to RANS
(Reynolds-Averaged Navier–Stokes). If turbulent flow is activated, you can set the
Turbulence model either to one of the algebraic turbulence models, Algebraic yPlus (the
default) or L-VEL, or to one of the following two-equation turbulence models: k-ε, Low
Reynolds Number k-ε. The Wall treatment is set to Automatic (default) or Low Re while
Wall functions is the only option for k-ε. For more information about turbulence
modeling, see Theory for the Turbulent Flow Interfaces in the CFD Module User’s
Guide.

DEPENDENT VARIABLES
The following dependent variables (fields) are defined for this physics interface — the
Velocity field u (SI unit: m/s) and its components, and the Pressure p (SI unit: Pa).

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

THE BRINKMAN EQUATIONS INTERFACE | 599

 The Use pseudo time stepping for stationary equation form option adds pseudo time
derivatives to the equation when the Stationary equation form is used in order to speed
up convergence. When selected, a CFL number expression should also be defined. For
the default Automatic option, the local CFL number (from the Courant–Friedrichs–
Lewy condition) is determined by a PID regulator.

• Domain, Boundary, Point, and Pair Nodes for the Brinkman Equations
Interface
• Theory for the Brinkman Equations Interface

In the COMSOL Multiphysics Reference Manual:

• Pseudo Time Stepping for Laminar Flow Models and Pseudo Time
Stepping
• Numerical Stability — Stabilization Techniques for Fluid Flow
• Discontinuous Galerkin Formulation

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

Equations Interface
The Brinkman Equations Interface has the following domain, boundary, point, and
pair nodes, listed in alphabetical order, available from the Physics ribbon toolbar
(Windows users), Physics context menu (Mac or Linux users), or right-click to access
the context menu (all users).

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

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

These nodes are described in this section:

• Porous Medium • Volume Force

• Initial Values • Fluid Properties
• Mass Source

600 | CHAPTER 7: FLUID FLOW INTERFACES

The following nodes (listed in alphabetical order) are described for the Laminar Flow
interface in the COMSOL Multiphysics Reference Manual:

• Flow Continuity • Periodic Flow Condition

• Inlet • Point Mass Source
• Line Mass Source • Pressure Point Constraint
• Boundary Stress • Symmetry
• Outlet • Wall
• Open Boundary

In the COMSOL Multiphysics Reference Manual see Table 2-4 for links
to common sections and Table 2-5 to common feature nodes. You can
also search for information: press F1 to open the Help window or Ctrl+F1
to open the Documentation window.

Porous Medium
The Porous Medium node adds the Brinkman equations: Equation 4-27 and
Equation 4-28 (excluding any mass sources). It has two default subfeatures — the
Fluid subfeature where the fluid density ρ(SI unit: kg/m3) and dynamic viscosity μ (SI
unit: Pa·s) are defined and the Porous Matrix subfeature where the permeability κ (SI
unit: m2) and porosity εp (dimensionless) are specified.

COORDINATE SYSTEM SELECTION

Select a coordinate system from the Coordinate system list for the interpretation of
directions in anisotropic material properties. The default is the Global coordinate
system, and the list contains any additional orthonormal coordinate system (except
boundary coordinate systems) added under the Definitions node.

The subnodes inherit these coordinate system settings. In particular, the Permeability
(in the Porous Matrix subnode) should be set according to the coordinate system
selected in this section.

THE BRINKMAN EQUATIONS INTERFACE | 601

 FLOW MODEL
Define if the flow follows a linear or nonlinear pressure-velocity relationship.

• Darcian flow (default) defines a linear relationship characteristic for low Reynolds
number laminar flows.
• Non-Darcian flow defines a nonlinear relationship due to inertial or turbulence
effects.

POROUS MEDIUM TURBULENCE MODEL

If in the parent feature node a turbulence model other than Algebraic yPlus or L-VEL is
selected, define a model which complements the basic turbulence model and accounts
for the influence of the porous matrix on turbulent flow in porous media.

• For Default and Nakayama-Kuwahara specify the Coefficient of subgrid turbulence

generation by porous matrix Cstpm which by default is set to 0.212.
• For Pedras-de Lemos, specify the Choice of the Pedras-de Lemos model coefficient.
When User defined is chosen, specify the Coefficient of subgrid turbulence generation
by porous matrix Cstpm with default value 0.212. Choosing Original results in
C stpm = 0.28 ⋅ ε p , while choosing Recalibrated results in C stpm = 0.18 .

DISTANCE EQUATION
This section is available for the turbulence models Algebraic yPlus or L-VEL. Select how
the Reference length scale lref (SI unit: m) is defined — Automatic (default) or Manual:

• For Automatic the wall distance is automatically evaluated to one tenth of the
shortest side of the geometry bounding box. This is usually quite accurate but it can
sometimes give a too high value if the geometry consists of several slim entities. In
such cases, define the reference length scale manually.
• For Manual it defines a different value or expression for the length scale. The default
is 1 m.

lref controls the result of the distance equation. Objects that are much smaller than lref
are effectively be diminished while the distance to objects much larger than lref are
accurately represented.

Fluid
This node defines the material properties of the fluid of the Porous Medium parent
node.

602 | CHAPTER 7: FLUID FLOW INTERFACES

MODEL INPUT
This section contains fields and values that are inputs for expressions defining material
properties. If such user-defined property groups are added, the model inputs appear
here.

FLUID PROPERTIES
Specify the Density ρ and the Dynamic viscosity μ (SI unit: Pa·s) of the fluid. The
defaults use values From material, for User defined enter a value or expression.

The dynamic viscosity describes the relationship between the shear stresses and the
shear rate in a fluid. Intuitively, water and air have a low viscosity, and substances often
described as thick, such as oil, have a higher viscosity.

Porous Matrix
This node defines the porosity and material properties of the solid matrix of the Porous
Medium parent node.

MODEL INPUT
This section contains fields and values that are inputs for expressions defining material
properties. If such user-defined property groups are added, the model inputs appear
here.

MATRIX PROPERTIES
The Porosity εp (a dimensionless number between 0 and 1) uses by default the value
From material. For User defined the default value is 1.

Select a Permeability model to specify the capacity of the porous material to transmit
flow. Depending on the Flow model selection in the parent Porous Medium feature node
you can choose between the following options:

• Permeability (the default) to directly enter the permeability of the porous matrix or
Kozeny-Carman to define the permeability from the porosity and mean Particle
diameter for Darcian flow or
• Forchheimer or Ergun for Non-Darcian flow.

Note that some of these options are only available for certain modules. For a detailed
overview of the functionality available in each product, visit https://
www.comsol.com/products/specifications/.

THE BRINKMAN EQUATIONS INTERFACE | 603

 The default Permeability κ (SI unit: m2) uses the value From material, as defined by the
Porous material list. For User defined select Isotropic to define a scalar value or Diagonal
or Symmetric to define a tensor value.

For Kozeny-Carman, enter the mean Particle diameter dp (SI unit: m), the default value
is 0.5 mm.

In case a Non-Darcian flow model is chosen in the parent node, Forchheimer is the
default selection for the Permeability model. For Forchheimer, the default Permeability
κ (SI unit: m2) uses the value From material. Furthermore, the dimensionless
Forchheimer parameter cF can be defined. The default value is 0.55.

If Ergun is selected, enter the mean Particle diameter dp (default value: 0.5 mm). The
permeability κ is then calculated using Equation 2-4 in the Porous Media Flow
Module User’s Guide.

• About Darcian and Non-Darcian Flow in the Porous Media Flow

Module User’s Guide
• Permeability Models in the Porous Media Flow Module User’s Guide

Mass Source
The Mass Source node adds a mass source (or mass sink) Qm to the right-hand side of
the continuity equation: Equation 7-51. This term accounts for mass deposit and/or
mass creation in porous domains. The physics interface assumes that the mass
exchange occurs at zero velocity.

∂ ε
( ρ ) + ∇ ⋅ ( ρu ) = Q m (7-16)
∂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).

604 | CHAPTER 7: FLUID FLOW INTERFACES

Volume Force
Use the Volume Force node to specify the force F on the right-hand side of
Equation 7-52. It then acts on each fluid element in the specified domains.

ρ-  ∂u u
---- + ( u ⋅ ∇ ) ----- =
εp  ∂ t εp
(7-17)
1 T 2   –1 Q m
– ∇ p + ∇ ⋅ -----  μ ( ∇u + ( ∇u ) ) – --- μ ( ∇ ⋅ u )I  –  κ μ + -------
- u + F
εp  3   ε p2 

VOLUME FORCE
Enter the components of Volume force F (SI unit: N/m3).

Initial Values
The Initial Values node adds initial values for the velocity field and the pressure that can
serve as an initial condition for a transient simulation or as an initial guess for a
nonlinear solver.

INITIAL VALUES
Enter initial values or expressions for the Velocity field u (SI unit: m/s) and the Pressure
p (SI unit: Pa). The default values are 0 m/s and 0 Pa, respectively.

Fluid Properties
The Fluid Properties node adds the momentum and continuity equations to solve for
free flow in nonporous domains. The node also provides an interface for defining the
material properties of the fluid.

MODEL INPUTS
Fluid properties, such as density and viscosity, can be defined through user inputs,
variables or by selecting a material. For the latter option, additional inputs — for
example, temperature or pressure — may be required to define these properties.

Temperature
By default, the single-phase flow interfaces are set to model isothermal flow. Hence,
the Temperature is User defined and defaults to 293.15 K. If a Heat Transfer interface
is included in the component, the temperature may alternatively be selected from this
physics interface. All physics interfaces have their own tags (Name). For example, if a

THE BRINKMAN EQUATIONS INTERFACE | 605

 Heat Transfer in Fluids interface is included in the component, the Temperature (ht)
option is available.

Absolute Pressure
This input appears when a material requires the absolute pressure as a model input.
The absolute pressure is used to evaluate material properties, but it also relates to the
value of the calculated pressure field. There are generally two ways to calculate the
pressure when describing fluid flow: either to solve for the absolute pressure or for a
pressure (often denoted gauge pressure) that relates to the absolute pressure through
a reference pressure.

The choice of pressure variable depends on the system of equations being solved. For
example, in a unidirectional incompressible flow problem, the pressure drop over the
modeled domain is probably many orders of magnitude smaller than the atmospheric
pressure, which, when included, may reduce the stability and convergence properties
of the solver. In other cases, such as when the pressure is part of an expression for the
gas volume or the diffusion coefficients, it may be more convenient to solve for the
absolute pressure.

The default Absolute pressure pA is p+pref where p is the dependent pressure variable
from the Navier–Stokes equations, and pref is from the user input defined at the
physics interface level. When pref is nonzero, the physics interface solves for a gauge
pressure. If the pressure field instead is an absolute pressure field, pref should be set to
0.

The Absolute pressure field can be edited by clicking Make All Model Inputs Editable
( ) and entering the desired value in the input field.

FLUID PROPERTIES
If density variations with respect to pressure are to be included in the computations,
the flow must be set to compressible.

The Dynamic viscosity μ describes the relationship between the shear rate and the shear
stresses in a fluid. Intuitively, water and air have low viscosities, and substances often
described as thick (such as oil) have higher viscosities.

Gravity
The Gravity global feature is automatically added when Include gravity is selected at the
interface level in the Physical Model settings. It defines the gravity forces from the
Acceleration of gravity value. When a turbulence model that solves for the turbulent

606 | CHAPTER 7: FLUID FLOW INTERFACES

kinetic energy, k, is used, the option Include buoyancy-induced turbulence is available.
When selected, the Buoyancy contribution is by default set to Automatic from
multiphysics. Contributions are only obtained from multiphysics couplings that
support buoyancy-induced turbulence, such as Nonisothermal Flow. If the Buoyancy
contribution is switched to User defined, a text field for the Turbulent Schmidt number
appears. See also Theory for Buoyancy-Induced Turbulence in the CFD Module
User’s Guide.

This feature requires a specific license. For a detailed overview of the functionality
available in each product visit https://www.comsol.com/products/specifications/.

ACCELERATION OF GRAVITY
The Acceleration of gravity (SI unit m/s, default value −gconstez in 2D axial symmetry
and 3D and −gconstey in 2D) is used to define the gravity forces. It should be a global
quantity.

THE BRINKMAN EQUATIONS INTERFACE | 607

 Theory for the Laminar Flow and
Creeping Flow Interfaces
The theory for the Single-Phase Flow, Laminar Flow interface is described in this
section:

• General Single-Phase Flow Theory

• Compressible Flow
• Weakly Compressible Flow
• The Mach Number Limit
• Incompressible Flow
• The Reynolds Number
• Gravity
• Theory for the Wall Boundary Condition
• Prescribing Inlet and Outlet Conditions
• 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.

608 | 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

∂ρ
------ + ∇ ⋅ ( ρu ) = 0 (7-18)
∂t

∂u
ρ ------ + ρ ( u ⋅ ∇ )u = ∇ ⋅ [ – pI + K ] + F (7-19)
∂t

∂T T ∂ρ ∂p
ρC p  ------- + ( u ⋅ ∇ )T = – ( ∇ ⋅ q ) + K:S – ---- -------  ------ + ( u ⋅ ∇ )p + Q (7-20)
 ∂t  ρ ∂T p  ∂t 

where

• ρ is the density (SI unit: kg/m3)

• u is the velocity vector (SI unit: m/s)
• p is pressure (SI unit: Pa)
• I is the identity matrix (unitless)
• K is the viscous stress tensor (SI unit: Pa)
• F is the volume force vector (SI unit: N/m3)
• Cp is the specific heat capacity at constant pressure (SI unit: J/(kg·K))
• T is the absolute temperature (SI unit: K)
• q is the heat flux vector (SI unit: W/m2)
• Q contains the heat sources (SI unit: W/m3)
• S is the strain-rate tensor:

1
S = --- ( ∇u + ( ∇u ) T )
2

The operation “:” denotes a contraction between tensors defined by

a:b =   anm bnm (7-21)

n m

This is sometimes referred to as the double dot product.

Equation 7-18 is the continuity equation and represents conservation of mass.

Equation 7-19 is a vector equation which represents conservation of momentum.

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 609
 Equation 7-20 describes the conservation of energy, formulated in terms of
temperature. This is an intuitive formulation that facilitates boundary condition
specifications.

To close the equation system, Equation 7-18 through Equation 7-20, constitutive
relations are needed.

For a Newtonian fluid, which has a linear relationship between stress and strain, Stokes
(Ref. 1) deduced the following expression:

2
K = 2μS – --- μ ( ∇ ⋅ u )I (7-22)
3

The dynamic viscosity, μ (SI unit: Pa·s), for a Newtonian fluid is allowed to depend on
the thermodynamic state but not on the velocity field. All gases and many liquids can
be considered Newtonian.

For an inelastic non-Newtonian fluid, the relationship between stress and strain rate is
nonlinear, and an apparent viscosity is introduced instead of the dynamic viscosity.
Examples of non-Newtonian fluids are honey, mud, blood, liquid metals, and most
polymer solutions.

In theory, the same equations describe both laminar and turbulent flows. In practice,
however, the mesh resolution required to simulate turbulence with the Laminar Flow
interface makes such an approach impractical.

There are several books where derivations of the Navier–Stokes equations

and detailed explanations of concepts such as Newtonian fluids can be
found. See, for example, the classical text by Batchelor (Ref. 3) and the
more recent work by Panton (Ref. 4).

Many applications describe isothermal flows for which Equation 7-20 is decoupled
from Equation 7-18 and Equation 7-19.

2D AXISYMMETRIC FORMULATIONS
A 2D axisymmetric formulation of Equation 7-18 and Equation 7-19 requires ∂ ⁄ ∂φ
to be zero. That is, there must be no gradients in the azimuthal direction. A common
additional assumption is, however, that u φ = 0 . In such cases, the φ -equation can be
removed from Equation 7-19. The resulting system of equations is both easier to
converge and computationally less expensive compared to retaining the φ -equation.

610 | CHAPTER 7: FLUID FLOW INTERFACES

The default 2D axisymmetric formulation of Equation 7-18 and Equation 7-19
therefore assumes that

∂ ⁄ ∂φ = 0
uφ = 0

Compressible Flow
The equations of motion for a single-phase fluid are the continuity equation:

∂ρ
------ + ∇ ⋅ ( ρu ) = 0 (7-23)
∂t

and the momentum equation:

∂u
ρ ------ + ρu ⋅ ∇u = – ∇p + ∇ ⋅  μ ( ∇u + ( ∇u ) T ) – --- μ ( ∇ ⋅ u )I + F
2
(7-24)
∂t  3 

These equations are applicable for incompressible as well as for compressible flow with
density and viscosity variations.

Weakly Compressible Flow

The same equations as for Compressible Flow are applied for weakly compressible flow.
The only difference is that the density is evaluated at the reference pressure. The
density may be a function of other quantities, in particular it may be temperature
dependent.

The weakly compressible flow equations are valid for incompressible as well as
compressible flow with density variations independent of the pressure.

Provided that the densities dependency pressure is specified through model inputs, the
density is automatically evaluated at the reference pressure level.

The Mach Number Limit

An important dimensionless number in fluid dynamics is the Mach number, Ma,
defined by

u
Ma = ------
a

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 611
 where a is the speed of sound. A flow is formally incompressible when Ma = 0. This is
theoretically achieved by letting the speed of sound tend to infinity. The Navier–Stokes
equations then have the mathematical property that pressure disturbances are
instantaneously propagated throughout the entire domain. This results in a parabolic
equation system.

The momentum equation, Equation 7-24, is parabolic for unsteady flow and elliptic
for steady flow, whereas the continuity equation, Equation 7-23, 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 7-24 becomes vanishingly
small, such as at an outflow boundary, in which case the momentum equation becomes
locally hyperbolic. The number of boundary conditions to apply on the boundary then
depends on the number of characteristics propagating into the computational domain.
For the purely hyperbolic system, the number of characteristics propagating from the
boundary into the domain changes as the Mach number passes through unity. Hence,
the number of boundary conditions required to obtain a numerically well-posed
system must also change. The compressible formulation of the laminar and turbulent
interfaces uses the same boundary conditions as the incompressible formulation, which
implies that the compressible interfaces are not suitable for flows with a Mach number
larger than or equal to one. Yet, the practical Mach number limit is lower than one.
The main reason is that the numerical scheme (stabilization and boundary conditions)
of the Laminar Flow interface does not recognize the direction and speed of pressure
waves. The fully compressible Navier–Stokes equations do, for example, start to display
very sharp gradients already at moderate Mach numbers. But the stabilization for the
single-phase flow interface does not necessarily capture these gradients. It is impossible
to give an exact limit where the low Mach number regime ends and the moderate
Mach number regime begins, but a rule of thumb is that the Mach number effects start
to appear at Ma = 0.3. For this reason, the compressible formulation is referred to as
Compressible flow (Ma<0.3) in COMSOL Multiphysics.

Incompressible Flow
When the temperature variations in the flow are small, a single-phase fluid can often
be assumed incompressible; that is, ρ is constant or nearly constant. This is the case for
all liquids under normal conditions and also for gases at low velocities. For constant ρ,
Equation 7-23 reduces to

ρ∇ ⋅ u = 0 (7-25)

612 | CHAPTER 7: FLUID FLOW INTERFACES

and Equation 7-24 becomes

∂u T
ρ + ρ ( u ⋅ ∇ )u = ∇ ⋅ [ – pI + μ ( ∇u + ( ∇u ) ) ] + F (7-26)
∂t

Provided that the densities dependency on temperature and pressure is specified

through model inputs, the density is evaluated at the reference pressure level and at the
reference temperature. However, if the density is a function of other quantities such as
a concentration field, or if the density is specified by a user defined expression, the user
has to make sure that the density is defined as constant when the incompressible flow
formulation is used.

The Reynolds Number

A fundamental characteristic in analyses of fluid flow is the Reynolds number:

ρUL
Re = ------------
μ

where U denotes a velocity scale, and L denotes a representative length. The Reynolds
number represents the ratio between inertial and viscous forces. At low Reynolds
numbers, viscous forces dominate and tend to damp out all disturbances, which leads
to laminar flow. At high Reynolds numbers, the damping in the system is very low,
giving small disturbances the possibility to grow by nonlinear interactions. If the
Reynolds number is high enough, the flow field eventually ends up in a chaotic state
called turbulence.

Note that the Reynolds number can have different meanings depending on the length
scale and velocity scale. To be able to compare two Reynolds numbers, they must be
based on equivalent length and velocity scales.

The Fluid Flow interfaces automatically calculate the local cell Reynolds number
Rec = ρ|u|h/(2μ) using the element length h for L and the magnitude of the velocity
vector u for the velocity scale U. This Reynolds number is not related to the character
of the flow field, but to the stability of the numerical discretization. The risk for
numerical oscillations in the solution increases as Rec grows. The cell Reynolds
number is a predefined quantity available for visualization and evaluation (typically it
is available as: spf.cellRe).

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 613
 Gravity

DEFINITION
The gravity force is defined from the acceleration of gravity vector, g, and the density,
ρ. Under usual conditions and in Cartesian coordinates with the z-axis in the vertical
direction,

 0 
 
g =  0 .
 
 – g const 

When gravity is considered, a volume force equal to ρg is included in the momentum

equation. For example, for laminar weakly compressible flow, it reads:

∂u
ρ ------ + ρu ⋅ ∇u = ∇ ⋅  – pI + μ ( ∇u + ( ∇u ) T ) – --- μ ( ∇ ⋅ u )I + F + ρg
2
(7-27)
∂t 3

Introducing a constant reference density ρref, and assuming that g is homogeneous,

this equation is equivalently written:

∂u
ρ ------ + ρu ⋅ ∇u=
∂t
(7-28)
∇ ⋅  – pI + μ ( ∇u + ( ∇u ) T ) – --- μ ( ∇ ⋅ u )I + ρ ref g ⋅ ( r – r ref ) + F + ( ρ – ρ ref )g
2
3

where r is the position vector and rref is an arbitrary reference position vector.

From this equation, it is convenient to define the reduced pressure which accounts for
the hydrostatic pressure, p˜ = p – ρ ref g ⋅ ( r – r ref )

∂u
ρ ------ + ρu ⋅ ∇u = ∇ ⋅  – p˜ I + μ ( ∇u + ( ∇u ) T ) – --- μ ( ∇ ⋅ u )I +
2
∂t  3  (7-29)
F + ( ρ – ρ ref )g

In Equation 7-29, the gravity force is written ( ρ – ρ ref )g .

PRESSURE FORMULATION
When the relative pressure is used (default option) the interface dependent variable
represents the relative pressure and the absolute pressure is defined as p A = p ref + p .
When the pressure is used to define a boundary condition (for example, when p0

614 | CHAPTER 7: FLUID FLOW INTERFACES

defines the pressure condition at an outlet), it represents the relative pressure. Hence
defining the outlet pressure as p hydro, approx = – ρ ref g ⋅ ( r – r ref ) compensates for the
gravity force for an ambient reference pressure of 0 Pa when the density is constant,
there is no external force, and provided pref, g and r0 are defined consistently.

When the reduced pressure is used, the interface dependent variable (named p by
default) represents the reduced pressure. The absolute pressure is then defined as
p A = p ref – ρ ref g ⋅ ( r – r ref ) + p . In this case when the pressure is used to define a
boundary condition (for example, to define a pressure condition at an outlet), its value
corresponds to the reduced pressure. Hence, the prescribed pressure compensates for
an approximate hydrostatic pressure, p hydro, approx = – ρ ref g ⋅ ( r – r ref ) which is exact
only when the density is constant and there is no external force.

PRESSURE BOUNDARY CONDITION

For an immobile fluid the momentum equation simplifies to ∇ ⋅ ( pI ) = F + ρg or

∇ ⋅ ( – p˜ I ) = F + ( ρ – ρ ref )g depending on the pressure formulation.

For incompressible flow, assuming there are no external forces, this leads respectively
to p = – ρ ref g ⋅ ( r – r ref ) + p 0 or p˜ = p 0 .

Theory for the Wall Boundary Condition

See Wall for the node settings.

SLIP
The Slip condition assumes that there are no viscous effects at the slip wall and hence,
no boundary layer develops. From a modeling point of view, this is a reasonable
approximation if the important effect of the wall is to prevent fluid from leaving the
domain. Mathematically, the constraint can be formulated as:

u ⋅ n = 0, ( – pI + μ ( ∇u + ( ∇u ) T ) )n = 0

The no-penetration term takes precedence over the Neumann part of the condition
and the above expression is therefore equivalent to

u ⋅ n = 0, K n – ( K n ⋅ n )n = 0
K n = μ ( ∇u + ( ∇u ) T )n

expressing that there is no flow across the boundary and no viscous stress in the
tangential direction.

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 615
 For a moving wall with translational velocity utr, u in the above equations is replaced
by the relative velocity urel = u−utr.

POROUS SLIP
The Porous slip option, which can be chosen in the Porous treatment of no slip condition
list when Enable porous media domains is activated, results in a special treatment of Wall
boundaries and Interior Wall boundaries adjacent to porous domains (Porous Medium
feature). Namely, similar to the Navier slip boundary condition, no penetration and
tangential stress conditions are applied at the wall:

μ u slip
u ⋅ n = 0, K n – ( K n ⋅ n )n = – ----- ---------- ,
ε p y ps
μ T
u slip = u – ( u ⋅ n )n , K n = ----- ( ∇u + ( ∇u ) )n
εp

Here, K n is the viscous wall traction, n is the wall normal, u slip is the tangential
velocity at the wall while real no slip is assumed to be applied at a distance d w
(half-height of the first cell adjacent to the wall) outside the wall, and y ps is the porous
slip length. An analytical derivation of the velocity profile in the boundary layer where
the pressure gradient is balanced by the sum of the Darcy term, the Forchheimer drag,
and the viscous term (neglecting convective terms) leads to the following expression
for y ps :

 1 + X e – ξp  1 + X e – ξp 2 d l pore

ξ
= l̃  --------------------------  -------------------------- e p – 1 ,
p p w
y ps

ξ p = ------ , l̃ = ------------------------,
–ξ p  1 + X p  l̃ 1 + 2c β
 1 – Xp e 

1 + 2c β – 1 + 4--- c β 1 + 4c D – 1 β ND κ 2
3 -
--------------------------------------------------
Xp = , c β = -------------------------------- , c D = ----------- ------ ∇p - ρg
2 μ μ
1 + 2c β + 1 + 4--- c β
3

where l pore = κ ⁄ ε p is the porous length scale, β ND = ρc F ⁄ κ is the non-Darcian

coefficient ( c F is the Forchheimer coefficient), g is the gravity vector, and
ξ p ,˜l ,X p ,c β ,c D are intermediate variables. This formula is used when the
Pressure-gradient formulation is chosen and it uses the pressure gradient at the wall. By
default, the Velocity formulation is activated and the corresponding formula is:

616 | CHAPTER 7: FLUID FLOW INTERFACES

 ξ w d l pore
y ps = l̃ ( e p – 1 ) , ξ p = ------ , l̃ = ------------------------,
l̃ 1 + 2c β
β ND κ u slip l pore 2 1⁄3
c β =  ---------------------------- ----------  ⁄ 2
 μ dw 

Although this formulation is an approximation, since it uses the slip velocity at the wall
to reconstruct the pressure gradient, it is rather accurate. Moreover, the influence of
the convective terms is partially accounted for in this formulation.

SLIDING WALL
The sliding wall option is appropriate if the wall behaves like a conveyor belt; that is,
the surface is sliding in its tangential direction. The wall does not have to actually move
in the coordinate system.

• In 2D, the tangential direction is unambiguously defined by the direction of the

boundary, but the situation becomes more complicated in 3D. For this reason, this
boundary condition has slightly different definitions in the different space
dimensions.
• For 2D and 2D axisymmetric components, the velocity is given as a scalar Uw and
the condition prescribes
u ⋅ n = 0, u ⋅ t = Uw

where t = (ny , −nx) for 2D and t = (nz, −nr) for axial symmetry.
• For 3D components, the velocity is set equal to a given vector uw projected onto
the boundary plane:
u w – ( n ⋅ u w )n
u = ---------------------------------------- u w
u w – ( n ⋅ u w )n

The normalization makes u have the same magnitude as uw even if uw is not exactly
parallel to the wall.

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

μ
K nt = – --- u slip
β

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

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

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 617
 The boundary condition does not set the tangential velocity component to zero;
however, the extrapolated tangential velocity component is 0 at a distance β outside
the wall.

The Slip Length setting is per default set to Factor of minimum element length. The slip
length β is then defined as β = f h h min , where h min is the smallest element side
(corresponds to the element size in the wall normal direction for boundary layer
elements) and f h is a user input.

In cases where the wall movement is nonzero, Account for the translational wall velocity
in the friction force may be selected to use ( u – u bnd – ( ( u – u bnd ) ⋅ n wall )n wall )
instead of u slip in the friction force. Then, the extrapolated tangential velocity
component is u bnd at a distance β outside of the wall. Note that the Velocity of sliding
wall uw is always accounted for in the friction force.

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

CONSTRAINT SETTINGS
The wall feature uses three different techniques to constraint the velocity field:

• Pointwise constraints is the standard technique to enforce strong constraints in the

finite element method. The desired value of the velocity is prescribed at each node
point in the mesh. Since the constraint is enforced locally at each node, only local
values are affected by the constraint and the constraints are independent of each
other. The solvers can therefore eliminate both the constrained degrees of freedom
and the constraint force terms, effectively reducing the number of degrees of
freedom being solved for.
The main advantage of pointwise constraints is that they enforce the constraint
exactly pointwise. This means that they do not introduce any leakage of the velocity
across the wall, unless specified. The main disadvantage of pointwise constraints is
that they introduce locking effects when trying to impose a no-penetration
condition for the velocity, u · n = 0, on curved walls or walls with sharp corners.
• Using Weak constraints is an alternative method to prescribe the velocity. It consists
on enforcing the boundary condition for the velocity via Lagrange multipliers.
Their main advantage is that the Lagrange multiplier can provide an accurate
representation of the reaction flux at the wall. Their main disadvantage is that they
introduce extra unknowns, and are usually difficult to combine with other constraint
methods on adjacent boundaries. Moreover, they may require extra constraints for

618 | CHAPTER 7: FLUID FLOW INTERFACES

 the Lagrange multipliers. For more information, see Weak Constraints in the
COMSOL Multiphysics Reference Manual.
• Discontinuous Galerkin (DG) constraints use a numerical flux to prescribe the
velocity at the wall. They impose the constraint in a integral sense rather than
pointwise, and do not suffer from the locking effects introduced by pointwise
constraints when trying to prescribe a no penetration condition for the velocity.
They are also better behaved when prescribing nonlinear constraints. Their main
disadvantage is that the constraint is only imposed approximately, and may produce
small leaks. For more information, see Discontinuous Galerkin Formulation.

The following combination of Constraint techniques can be selected in the Constraint

Setting sections of Wall boundary conditions:

• Use default settings. The default settings use different constraint methods
depending on whether only the normal component of the velocity is prescribed,
such as in the no penetration condition, u · n = 0, imposed, for example, in Slip
walls or No Slip walls using Wall Functions or Automatic Wall Treatment, or both
tangential and normal components are prescribed, as is the case of No Slip walls in
laminar flow.
DG constraints are used to impose the no penetration condition for Slip walls. When
a No Slip condition is prescribed, pointwise constraints are used except for moving
walls where DG constraints are used.
• Use Pointwise constraints.
• Use DG constraints.
• Use Weak constraints. Weak constraints are not available on Interior Walls.
• Use Mixed constraints. This option is only available when both the tangential and
normal components of the velocity need to be prescribed. The velocity on the wall
normal direction is imposed via pointwise constraints. The constraint for the
tangential directions is relaxed, and DG constraints are used instead. This provides
improved accuracy and performance when working with coarse boundary layer
meshes. For more information, see Ref. 18.

Prescribing Inlet and Outlet Conditions

The Navier–Stokes equations can show large variations in mathematical behavior,
ranging from almost completely elliptic to almost completely hyperbolic. This has
implications when it comes to prescribing admissible boundary conditions. There is

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 619
 also a discrepancy between mathematically valid boundary conditions and practically
useful boundary conditions. See Inlet and Outlet for the node settings.

INLET CONDITIONS
An inlet requires specification of the velocity components. The most robust way to do
this is to prescribe a velocity field using a Velocity condition.

A common alternative to prescribing the complete velocity field is to prescribe a

pressure and all but one velocity component. The pressure cannot be specified
pointwise because this is mathematically over-constraining. Instead the pressure can be
specified via a stress condition:

∂u n
– p + 2μ --------- = F n (7-30)
∂n

where ∂un/∂n is the normal derivative of the normal velocity component.

Equation 7-30 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 7-30 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 7-30, all but one
velocity component must be specified. For low Reynolds numbers, this can be specified
by a vanishing tangential stress condition:

∂u t
μ -------- = 0
∂n

which is what the Normal stress condition does. Vanishing tangential stress becomes a
less well-posed inlet condition as the Reynolds number increases. The Pressure
condition in the Inlet feature therefore requires a flow direction to be prescribed,
which provides a well-posed condition independent of Reynolds number.

OUTLET CONDITIONS
The most common approach is to prescribe a pressure via a normal stress condition on
the outlet. This is often accompanied by a vanishing tangential stress condition:

∂u t
μ -------- = 0
∂n

620 | CHAPTER 7: FLUID FLOW INTERFACES

where ∂ut/∂n is the normal derivative of the tangential velocity field. It is also possible
to prescribe ut to be zero. The latter option should be used with care since it can have
a significant effect on the upstream solution.

The elliptic character of the Navier–Stokes equations mathematically permits

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.

POINTWISE MASS FLUX

The pointwise mass flux sets the velocity at the boundary to:

mf
u = – ------- n
ρ

where mf is the normal mass flux and ρ is the density.

MASS FLOW RATE

The mass flow rate boundary condition sets the total mass flow through the boundary
according to:

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 621
 –  dbc ρ ( u ⋅ n ) dS = m
∂Ω

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 (7-31)

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:

ρ
–  dbc ρ------st- ( u ⋅ n ) dS = Qsv
∂Ω

where dbc (only present in the 2D component Cartesian axis system) is the boundary
thickness normal to the fluid-flow domain, ρst is the standard density, and Qsv is the
standard flow rate. The standard density is defined by one of the following equations:

Mn
ρ st = --------
Vn

p st M n
ρ st = ----------------
RT st

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 7-31 or Equation 7-32 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.

622 | CHAPTER 7: FLUID FLOW INTERFACES

Fully Developed Flow (Inlet)
The Fully developed flow boundary condition can be understood from the following
figure:

pinl Ω

The flow to the domain Ω is assumed to enter through a straight channel of length L.
The channel is a virtual extrusion of the inlet cross section and a pressure constant
pressure Pinl is applied on the inlet of the virtual channel.

The Fully Developed Flow boundary condition prescribes that the tangential flow
component on the boundary is zero:

u – ( u ⋅ n )n = 0

The momentum equation for a fully developed flow in the virtual extrusion of the inlet
cross section can then be projected onto the inlet boundary with the following weak
equation as the result:

( – μ ( ∇tu + ( ∇tu ) T ) + ( p + P inl ) ⁄ 2 ) ∇tûL – P inl ( n ⋅ û )

The exact value of L is somewhat arbitrary as long as it is not too high or too low. L is
therefore set to ten times the inlet edge length in 2D and to ten times the square root
of the inlet area in 2D axisymmetry and in 3D.

The fact that the velocity profile is not prescribed, but rather the solution of a projected
weak contribution, means that the actual velocity profile that is obtained on the inlet
can deviate from the analytical fully developed flow profile (in cases such an analytical
solution exists) if required by the solution inside the computational domain, Ω. This is
most notably if the flow is strongly curved just downstream of the inlet. This can, for
example, be the case if an object is positioned just downstream of the inlet or if the
adjacent boundaries are not orthogonal to the inlet. The analytical solution can in
these cases be recovered by including a little bit of the inlet channel in the
computational domain.

The inlet pressure, Pinl, must be solved for and the its equation is a discrete algebraic
equation (DAE) for Pinl. When, for example, the average velocity is specified, the DAE
reads

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 623
 (  u ⋅ n + U av )P̂ inl

where <⋅> denotes the average over the inlet. Since the equation for Pinl is a DAE (the
equation for Pinl does not contain Pinl), it must be solved coupled to Navier–Stokes
and it must be treated by a Vanka pre-smoother and post-smoother if iterative solvers
are used.

The boundary conditions for the virtual inlet channel are inherited from the
boundaries adjacent to the inlet channel. Virtual boundaries adjacent to walls (except
slip walls) are treated as no-slip walls. Virtual boundaries adjacent to any other type of
boundary are treated as slip-walls (or equivalently as symmetry boundaries). So in the
figure above, if the lower boundary of Ω is a no-slip wall and the top boundary is a
symmetry boundary, the lower boundary of the virtually extruded channel becomes a
no-slip wall and the upper boundary becomes a symmetry boundary.

Algebraic turbulence models need to additional equations or constraints. For all other
turbulence models, their weak equations in the virtual inlet channel are projected onto
the inlet of the computational domain. The projections are regularized to prevent the
production to fall to zero, so the solutions of the projects can show slight deviation
from the correct solutions close to no-slip walls.

Fully Developed Flow (Outlet)

The Fully developed flow boundary condition can be understood from the following
figure:

Ω pexit

The flow to the domain Ω is assumed to enter through a straight channel of length L.
The channel is a virtual extrusion of the inlet cross section and a pressure constant
pressure Pexit is applied on the inlet of the virtual channel.

The Fully Developed Flow boundary condition prescribes that the tangential flow
component on the boundary is zero:

u – ( u ⋅ n )n = 0

624 | CHAPTER 7: FLUID FLOW INTERFACES

The momentum equation for a fully developed flow in the virtual extrusion of the inlet
cross section can then be projected onto the inlet boundary with the following weak
equation as the result:

( – μ ( ∇tu + ( ∇tu ) T ) + ( p + P exit ) ⁄ 2 ) ∇tûL – P exit ( n ⋅ û )

The exact value of L is somewhat arbitrary as long as it is not too high or too low. L is
therefore set to ten times the inlet edge length in 2D and to ten times the square root
of the inlet area in 2D axisymmetry and in 3D.

The fact that the velocity profile is not prescribed, but rather the solution of a projected
weak contribution, means that the actual velocity profile that is obtained on the outlet
can deviate from the analytical fully developed flow profile (in cases such an analytical
solution exists) if required by the solution inside the computational domain, Ω. The
inlet pressure, Pexit, must be solved for and the its equation is a discrete algebraic
equation (DAE) for Pexit. When, for example, the average velocity is specified, the
DAE reads

(  u ⋅ n + U av )P̂ exit

where <⋅> denotes the average over the inlet. Since the equation for Pext is a DAE, it
must be solved coupled to Navier–Stokes and it must be treated by a Vanka
pre-smoother and post-smoother if iterative solvers are used.

The boundary conditions for the virtual outlet channel are inherited from the
boundaries adjacent to the outlet channel. Virtual boundaries adjacent to walls (except
slip walls) are treated as no-slip walls. Virtual boundaries adjacent to any other type of
boundary are treated as slip-walls (or equivalently as symmetry boundaries).

No Viscous Stress
For this module, and in addition to the Pressure, No Viscous Stress boundary
condition, the viscous stress condition sets the viscous stress to zero:

 μ ( ∇u + ( ∇u ) T ) – 2
--- μ ( ∇ ⋅ u )I n = 0
 3 

( μ ( ∇u + ( ∇u ) T ) )n = 0

using the compressible/weakly compressible and the incompressible formulation,

respectively.

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 625
 The condition is not a sufficient outlet condition since it lacks information about the
outlet pressure. It must hence be combined with pressure point constraints on one or
several points or lines surrounding the outlet.

This boundary condition is numerically the least stable outlet condition, but can still
be beneficial if the outlet pressure is nonconstant due to, for example, a nonlinear
volume force.

Normal Stress Boundary Condition

The total stress on the boundary is set equal to a stress vector of magnitude f0, oriented
in the negative normal direction:

 – pI +  μ ( ∇u + ( ∇u ) T ) – 2
--- μ ( ∇ ⋅ u )I  n = – f 0 n
  3 

( – pI + μ ( ∇u + ( ∇u ) T ) )n = – f 0 n

using the compressible/weakly compressible and the incompressible formulation,

respectively.

This implies that the total stress in the tangential direction is zero. This boundary
condition implicitly sets a constraint on the pressure which for 2D flows is

∂u n
p = 2μ ---------- + f 0 (7-32)
∂n

If ∂un/∂n is small, Equation 7-32 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.

Pressure Boundary Condition

For single-phase flow, a mathematically correct natural boundary condition for outlets
is

 – pI + μ ( ∇u + ( ∇u ) T ) – 2
--- μ ( ∇ ⋅ u )I n = – p 0 n (7-33)
 3 

( – pI + μ ( ∇u + ( ∇u ) T ) )n = – p 0 n (7-34)

626 | CHAPTER 7: FLUID FLOW INTERFACES

using the compressible/weakly compressible and the incompressible formulation,
respectively.

This is a normal stress condition together with a no-tangential-stress condition. When

μ > 0, Equation 7-33 or Equation 7-34 can be supplemented with a tangential velocity
condition

u⋅t = 0 (7-35)

If so, the no-tangential-stress condition is overridden. An issue with Equation 7-33 or

Equation 7-34 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

--- μ ( ∇ ⋅ u )I n = – pˆ 0 n
 – pI + μ ( ∇u + ( ∇u ) T ) – 2
 3 
, (7-36)
( – pI + μ ( ∇u + ( ∇u ) T ) )n = – pˆ 0 n
pˆ ≤ p
0 0

the normal stress is adjusted to keep

u⋅n≥0 (7-37)

Equation 7-36 effectively means that the prescribed pressure is p0 if u⋅n ≥ 0, but
smaller at locations where u⋅n < 0. This means that Equation 7-36 does not completely
prevent backflow, but the backflow is substantially reduced. Backflow is suppressed
also when external forces are acting on the fluid, provided the magnitude of these
forces are of the same order as the dynamic pressure at the outlet.

A pressure condition can also be applied at an inlet. In this case, either the normal stress
is prescribed

n  – pI + μ ( ∇u + ( ∇u ) T ) – --- μ ( ∇ ⋅ u )I n = – pˆ 0
T 2
 3 
(7-38)
n ( – pI + μ ( ∇u + ( ∇u ) T ) )n = – pˆ 0
T

pˆ ≥ p
0 0

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 627
 together with the tangential condition in Equation 7-35, or, a general flow direction
is prescribed.

--- μ ( ∇ ⋅ u )I n = – pˆ 0 ( r ⋅ n )
T  – pI + μ ( ∇u + ( ∇u ) T ) – 2
ru
 3  u
T ( – pI + μ ( ∇u + ( ∇u ) T ) )n = – p
ru ˆ (r ⋅ n)
0 u
(7-39)
pˆ ≥ 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 – --- ρ u (7-40)
2

The equation is imposed with two options: Average and Pointwise.

In the first option, pstat is prescribed by:

T T (7-41)
n ( – pI + μ ( ∇u + ( ∇u ) T ) )n = n ( – p stat I + μ ( ∇u + ( ∇u ) T ) )n

where ptot and |u|2 are averaged over the boundaries using the aveop operator:

1 2
p stat = aveop ( p tot ) – --- ρ ⋅ aveop ( u )
2

For the second option, Equation 7-40 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.

628 | CHAPTER 7: FLUID FLOW INTERFACES

Mass Sources for Fluid Flow
There are two types of mass sources in a Single-Phase Flow interface: point sources and
line sources.

These features require at least one of the following licenses: Battery

Design Module, CFD Module, Chemical Reaction Engineering Module,
Corrosion Module, Electrochemistry Module, Electrodeposition
Module, Fuel Cell & Electrolyzer Module, Microfluidics Module, Pipe
Flow Module, Polymer Flow Module, or Subsurface Flow Module.

POINT SOURCE
·
A point source is theoretically formed by taking a mass injection/ejection, Q (SI unit:
3
kg/(m ·s)), in a small volume δV and then letting the size of the volume tend to zero
while keeping the total mass flux constant. Given a point source strength, q· p (SI unit:
kg/s), this can be expressed as

·
lim Q = q· p (7-42)
δV → 0
δV

An alternative way to form a point source/sink is to assume that mass is injected/

extracted through the surface of a small object. Letting the object surface area tend to
zero while keeping the mass flux constant, results in the same point source. For this
alternative approach, effects resulting from the physical object volume, such as drag
and fluid displacement, need to be neglected.

The weak contribution

q· p test ( p )
·
is added to a point in the geometry. As can be seen from Equation 7-42, Q must tend
to plus or minus infinity as δV tends to zero. This means that in theory the pressure
also tends to plus or minus infinity.

Observe that “point” refers to the physical representation of the source. A point source
can therefore only be added to points in 3D components and to points on the
symmetry axis in 2D axisymmetry components. Other geometrical points in 2D
components represent physical lines.

The finite element representation of Equation 7-42 corresponds to a finite pressure in

a point with the effect of the point source spread out over a region around the point.

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 629
 The size of the region depends on the mesh and on the strength of the source. A finer
mesh gives a smaller affected region, but also a more extreme pressure value. It is
important not to mesh too finely around a point source since the resulting pressure can
result in unphysical values for the density, for example. It can also have a negative effect
on the condition number for the equation system.

LINE SOURCE
·
A line source can theoretically be formed by assuming a source of strength Q (SI unit:
kg/(m3·s)), located within a tube with cross-sectional area δS and then letting δS tend
to zero, while keeping the total mass flux per unit length constant. Given a line source
strength, q· l (SI unit: kg/(m·s)), this can be expressed as

· ·
lim
δS → 0  Q = ql (7-43)
δS

As in the point source case, an alternative approach is to assume that mass is injected/
extracted through the surface of a small object. This results in the same mass source,
but requires that effects on the fluid resulting from the physical object volume are
neglected.

The weak contribution

q· l test ( p )

is added to lines in 3D or to points in 2D (which represent cut-through views of lines).

Line sources can also be added to the axisymmetry line in 2D axisymmetry
components. It cannot, however, be added to geometrical lines in 2D because they
represent physical planes.

As with a point source, it is important not to mesh too finely around the line source.

For feature node information, see Line Mass Source and Point Mass
Source.

630 | CHAPTER 7: FLUID FLOW INTERFACES

 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 7-24 or Equation 7-26) 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, Δt

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 631
 (see, for example, Ref. 9 and Ref. 10). This simple approach does not, however,
necessarily reflect on the actual time-scales in the physics. A typical example is reacting
flows where the time step is often guided by fast reactions, while the flow develops
relatively slowly. The COMSOL Multiphysics software can therefore replace Δt2 in the
time-scale tensor with measures of type ( 1 ⁄ ( Δt̃ ) 2 ) –1 , which are calculated from
projections of weak expressions in a fashion similar to those in Ref. 11. These measures
of the time scale are used when Use dynamic subgrid time scale check box is selected.
Streamline diffusion is active by default because it is necessary when convection is
dominating the flow.

The governing equations for incompressible flow are subject to the Babuška–Brezzi
condition, which states that the shape functions (basis functions) for pressure must be
of lower order than the shape functions for velocity. If the incompressible Navier–
Stokes equations are stabilized by streamline diffusion, it is possible to use equal-order
interpolation. Hence, streamline diffusion is necessary when using first-order elements
for both velocity and pressure. This applies also if the model is solved using geometric
multigrid (either as a solver or as a preconditioner) and at least one multigrid hierarchy
level uses linear Lagrange elements.

CROSSWIND DIFFUSION
Crosswind diffusion can also be formulated for systems of equations, and when applied
to the Navier–Stokes equations it becomes a shock-capturing operator. COMSOL
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.

632 | CHAPTER 7: FLUID FLOW INTERFACES

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.

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 633
 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

634 | CHAPTER 7: FLUID FLOW INTERFACES

default smoother for higher order elements is an SOR Line smoother. SOR Line
handles mesh anisotropy but does not formally address the saddle point character. It
does, however, function in practice provided that streamline diffusion and crosswind
diffusion are both active.

A different kind of saddle point character can arise if the equation system contains
ODE variables. Some advanced boundary conditions can add equations with such
variables. These variables must be treated with the Vanka algorithm. SCGS includes an
option to invoke Vanka. Models with higher-order elements must apply SCGS or use
the Vanka smoother. The latter is the default suggestion for higher-order elements, but
it does not work optimally for anisotropic meshes.

TIME-DEPENDENT SOLVERS
The default time-dependent solver for Navier–Stokes is the BDF method with
maximum order set to two. Higher BDF orders are not stable for transport problems
in general nor for Navier–Stokes in particular.

BDF methods have been used for a long time and are known for their stability.
However, they can have severe damping effects, especially the lower-order methods.
Hence, if robustness is not an issue, a model can benefit from using the generalized-α
method instead. Generalized-α is a solver that has properties similar to those of the
second-order BDF solver but it is much less diffusive.

Both BDF and generalized-α are per default set to automatically adjust the time step.
While this works well for many models, extra efficiency and accuracy can often be
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 7-26
reduces to:

T
ρ ( u ⋅ ∇ )u = ∇ ⋅ [ – pI + μ ( ∇u + ( ∇u ) ) ] + F (7-44)

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 635
 Solving Equation 7-44 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 7-44:

u – nojac ( u ) T
ρ ------------------------------- + ρ ( u ⋅ ∇ )u = ∇ ⋅ [ – pI + μ ( ∇u + ( ∇u ) ) ] + F
Δt̃

where Δt̃ is a pseudo time step. Since u−nojac(u) is always zero, this term does not
affect the final solution. It does, however, affect the discrete equation system and
effectively transforms a nonlinear iteration into a step of size Δt̃ of a time-dependent
solver.

Pseudo time stepping is not active per default. The pseudo time step Δt̃ can be chosen
individually for each element based on the local CFL number:

h
Δt̃ = CFL loc ------
u

where h is the mesh cell size. A small CFL number means a small time step. It is
practical to start with a small CFL number and gradually increase it as the solution
approaches steady state.

If the automatic expression for CFLloc is set to the built-in variable CFLCMP, then the
automatic setting suggests a PID regulator for the pseudo time step in the default
solver. The PID regulator starts with a small CFL number and increases CFLloc as the
solution comes closer to convergence.

The default manual expression is

1.3 min ( niterCMP, 9 ) +

if ( niterCMP > 20, 9 ⋅ 1.3 min ( niterCMP – 20, 9 ), 0 ) + (7-45)
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

636 | CHAPTER 7: FLUID FLOW INTERFACES

then takes it to 1060. Equation 7-45 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
d x
= F  t, x, 
dx
m
dt2 dt

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 637
 where x is the position of the particle, m the particle mass, and F is the sum of all forces
acting on the particle. Examples of forces acting on a particle in a fluid are the drag
force, the buoyancy force, and the gravity force. The drag force represents the force
that a fluid exerts on a particle due to a difference in velocity between the fluid and the
particle. It includes the viscous drag, the added mass, and the Basset history term.
Several empirical expressions have been suggested for the drag force. One of those is
the one proposed by Khan and Richardson (Ref. 13). That expression is valid for
spherical particles for a wide range of particle Reynolds numbers. The particle
Reynolds number is defined as

u – u p 2rρ
Re p = ----------------------------
μ

where u is the velocity of the fluid, up the particle velocity, r the particle radius, ρ the
fluid density, and μ the dynamic viscosity of the fluid. The empirical expression for the
drag force according to Khan and Richardson is

2 -0.31 3.45
F = πr ρ u – u p ( u – u p ) [ 1.84Re p + 0.293Re p0.06 ]

The model Flow Past a Cylinder (Application Library path

COMSOL_Multiphysics/Fluid_Dynamics/cylinder_flow) demonstrates how to
add and set up particle tracing in a plot group using the Particle Tracing
with Mass node. It uses the predefined Khan-Richardson model for the
drag force and neglects gravity and buoyancy forces.

References for the Single-Phase Flow, Laminar Flow Interfaces

1. G.G. Stokes, Trans. Camb. Phil. Soc., vol. 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,” Comput. Methods Appl. Mech. Eng., vol. 97,
pp. 157–192, 1992.

638 | CHAPTER 7: FLUID FLOW INTERFACES

6. Y. Bazilevs, V.M. Calo, T.E. Tezduyar, and T.J.R. Hughes, “YZβ Discontinuity
Capturing for Advection-dominated Processes with Application to Arterial Drug
Delivery,” 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,” Comput. Methods Appl. Mech. Eng.,
vol. 58, pp. 305–328, 1986.

9. G. Hauke and T.J.R. Hughes, “A Unified Approach to Compressible and

Incompressible Flows,” Comput. Methods Appl. Mech. Eng., vol. 113, pp. 389–395,
1994.

10. G. Hauke, “Simple Stabilizing Matrices for the Computation of Compressible

Flows in Primitive Variables”, Comput. Methods Appl. Mech. Eng., 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,” Comput. Methods Appl. Mech. Eng., 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,” Comput. Methods Appl. Mech. Eng., 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. Comput. Appl. Math., 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,” Comput. Fluids, vol. 36, pp. 12–26, 2007.

THEORY FOR THE LAMINAR FLOW AND CREEPING FLOW INTERFACES | 639
640 | CHAPTER 7: FLUID FLOW INTERFACES
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

THEORY FOR THE DARCY’S LAW INTERFACE | 641

 boundary conditions and result evaluation using hydraulic head and pressure head. In
the physics interface, pressure is always the dependent variable.

Darcy’s Law — Equation Formulation

Darcy’s law states that the velocity field is determined by the pressure gradient, the
fluid viscosity, and the structure of the porous medium:

κ
u = – --- ∇p (7-46)
μ

In this equation, u is the Darcy’s velocity or specific discharge vector (SI unit: m/s);
κ is the permeability of the porous medium (SI unit: m2); μ is the fluid’s dynamic
viscosity (SI unit: Pa·s); p is the pore pressure (SI unit: Pa) and ρ is the density of the
fluid (SI unit: kg/m3).

• The above equation formulation is called linear Darcy law. The

applicability of this formulation is discussed in the chapter About
Darcian and Non-Darcian Flow in the Porous Media Flow Module
User’s Guide.
• Permeability can be defined in different ways, either directly or based
on predefined permeability models. These are described in detail in the
chapter Permeability Models.
• For a detailed overview of the permeability models available in each
product visit https://www.comsol.com/products/specifications/.

The Darcy’s Law interface combines Darcy’s law with the continuity equation

∂ ρε
( p ) + ∇ ⋅ ( ρu ) = Q m (7-47)
∂t

In the above equation, ρ is the fluid density (SI unit: kg/m3), εp is the porosity, and
Qm is a mass source term (SI unit: kg/(m3·s)). Porosity is defined as the fraction of
the control volume that is occupied by pores. Thus, the porosity can vary from zero
for pure solid regions to unity for domains of free flow.

For large-scale applications it might be necessary to take gravity effects into account.
Darcy’s law then applies when the gradient in hydraulic potential drives fluid
movement in the porous medium. Darcy’s law then has the form:

642 | CHAPTER 7: FLUID FLOW INTERFACES

 κ
u = – --- ( ∇p – ρ g ) (7-48)
μ

• See the section Gravity Effects in the Subsurface Flow Module User’s
Guide.
• Note that gravity effects are only included in some modules. For a
detailed overview of the functionality available in each product visit
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 7-46) into the continuity equation produces the
generalized governing equation

∂ ρε κ
( p ) + ∇ ⋅ ρ – --- ( ∇p ) = Q m (7-49)
∂t μ

Represent this equation fully in COMSOL Multiphysics because relationships between

density or permeability can be freely specified, for example, and pressure, temperature,
concentration, and so on.

Expand the time-derivative term in Equation 7-49

∂ ρε = ∂-----
ρ ∂ε p
( p) ε p - + ρ --------
∂t ∂t ∂t

Define the porosity and the density as functions of the pressure, and apply the chain
rule

∂ρ ∂ε p ∂ρ ∂p ∂ε p ∂p
ε p ------ + ρ -------- = ε p ------ ------ + ρ -------- ------
∂t ∂t ∂p ∂t ∂p ∂t

Insert the definition of fluid compressibility χf = (1/ρ)(∂ρ/∂p) to the right-hand side and
rearrange to arrive at

∂( ρε p ) ∂ε p ∂p ∂p
---------------- = ρ  ε p χ f + -------- ------ = ρS ------
∂t  ∂p  ∂t ∂t

THEORY FOR THE DARCY’S LAW INTERFACE | 643

 Using this relation, the generalized governing equation (Equation 7-49) takes the
following form:

∂p κ
ρS ------ + ∇ ⋅ ρ – --- ( ∇p ) = Q m (7-50)
∂t μ

In this equation, S is the storage coefficient (SI unit: 1/Pa), which can be interpreted
as the weighted compressibility of the porous material and the fluid. The storage S can
be an expression involving results from a solid-deformation equation or an expression
involving temperatures and concentrations from other analyses. The Darcy’s Law
interface implements Equation 7-50 in the Porous Medium node, which explicitly
includes different storage models to choose from, such as linearized storage which
defines S (SI unit: 1/Pa) using the compressibility of fluids χf and of the porous matrix
χp:

S = ε p χ f + ( 1 – ε p )χ p ,

or the poroelastic storage where

S = εp χf .

The Storage Model node is only available for the Subsurface Flow
Module and the Porous Media Flow Module. For a detailed overview of
the functionality available in each product visit https://
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, uα, (also termed the seepage velocity) defined as uα = u/εp, where εp is the
porosity.

References for the Darcy’s Law Interface

1. J. Bear, Hydraulics of Groundwater, McGraw-Hill, 1979.

644 | CHAPTER 7: FLUID FLOW INTERFACES

2. S.E. Ingebritsen and W.E. Sanford, Groundwater in Geologic Processes, Cambridge
University Press, 1998.

3. N.H. Sleep and K. Fujita, Principles of Geophysics, Blackwell Science, 1997.

4. D.L. Turcotte and G. Schubert, Geodynamics, Cambridge University Press, 2002.

5. J. Bear, Dynamics of Fluids in Porous Media, Elsevier Scientific Publishing, 1972.

6. Ö. Akgiray and A.M. Saatçı, “A New Look at Filter Backwash Hydraulics,” Water
Science and Technology: Water Supply, vol. 1, no. 2, pp. 65–72, 2001.

7. L. Klinkenberg, “The permeability of porous media to liquids and gases,” Drilling

and Production Practice, Am. Petroleum Inst., pp. 200–213, 1941.

8. Yu-Shu Wu and others, “Gas Flow in Porous Media with Klinkenberg Effects,”
Transport in Porous Media, vol. 32, pp. 117–137, 1998.

THEORY FOR THE DARCY’S LAW INTERFACE | 645

 Theory for the Free and Porous
Media Flow Interface
The Free and Porous Media Flow Interface uses the Navier–Stokes equations to
describe the flow in open regions, and the Brinkman equations to describe the flow in
porous regions.

The same fields, u and p, are solved for in both the free flow domains and in the porous
domains. This means that the pressure in the free fluid and the pressure in the pores is
continuous over the interface between a free flow domain and a porous domain. It also
means that continuity is enforced between the fluid velocity in the free flow and the
Darcy velocity in the porous domain. This treatment is one of several possible models
for the physics at the interface. Examples of other models can be found in Ref. 1.

The continuity in u and p implies a stress discontinuity at the interface between a

free-flow domain and a porous domain. The difference corresponds to the stress
absorbed by the rigid porous matrix, which is a consequence implicit in the
formulations of the Navier–Stokes and Brinkman equations.

Reference for the Free and Porous Media Flow Interface

1. M.L. Bars and M.G. Worster, “Interfacial Conditions Between a Pure Fluid and a
Porous Medium: Implications for Binary Alloy Solidification,” J. Fluid Mech.,
vol. 550, pp. 149–173, 2006.

646 | CHAPTER 7: FLUID FLOW INTERFACES

Theory for the Brinkman Equations
Interface
The Brinkman Equations Interface theory is described in this section:

• About the Brinkman Equations

• Brinkman Equations Theory
• References for the Brinkman Equations Interface

About the Brinkman Equations

In porous domains, the flow variables and fluid properties are defined at any point
inside the medium by means of averaging of the actual variables and properties over a
certain volume surrounding the point. This control volume must be small compared
to the typical macroscopic dimensions of the problem, but it must be large enough to
contain many pores and solid matrix elements.

Porosity is defined as the fraction of the control volume that is occupied by pores.
Thus, the porosity can vary from zero for pure solid regions to unity for domains of
free flow.

The physical properties of the fluid, such as density and viscosity, are defined as
intrinsic volume averages that correspond to a unit volume of the pores. Defined this
way, they present the relevant physical parameters that can be measured experimentally,
and they are assumed to be continuous with the corresponding parameters in the
adjacent free flow.

The flow velocity is defined as a superficial volume average, and it corresponds to a

unit volume of the medium including both the pores and the matrix. It is sometimes
called the Darcy velocity, defined as the volume flow rate per unit cross section of the
medium. Such a definition makes the velocity field continuous across the boundaries
between porous regions and regions of free flow.

Brinkman Equations Theory

The dependent variables in the Brinkman equations are the Darcy velocity and the
pressure. The flow in porous media is governed by a combination of the continuity
equation and the momentum equation, which together form the Brinkman equations:

THEORY FOR THE BRINKMAN EQUATIONS INTERFACE | 647

 ∂ ε
( ρ ) + ∇ ⋅ ( ρu ) = Q m (7-51)
∂t p

ρ-  ∂u
+ ( u ⋅ ∇ ) ----- =
---- u
εp  ∂ t εp
(7-52)
1 T 2   –1 Q m
–∇ p + ∇ ⋅ ----
- --
- --------
μ ( ∇u + ( ∇u ) ) – μ ( ∇ ⋅ u )I  –  κ μ + 2  u + F
ε p  3   εp 

In these equations:

• μ (SI unit: kg/(m·s)) is the dynamic viscosity of the fluid

• u (SI unit: m/s) is the velocity vector
• ρ (SI unit: kg/m3) is the density of the fluid
• p (SI unit: Pa) is the pressure
• εp is the porosity
• κ (SI unit: m2) is the permeability of the porous medium, and
• Qm (SI unit: kg/(m3·s)) is a mass source or sink

Influence of gravity and other volume forces can be accounted for via the force term
F (SI unit: kg/(m2·s2)).

When the Neglect inertial term (Stokes flow) check box is selected, the term (u · ∇)(u/
εp) on the left-hand side of Equation 7-52 is disabled.

The mass source, Qm, accounts for mass deposit and mass creation within the domains.
The mass exchange is assumed to occur at zero velocity.

The Forchheimer and Ergun drag options add a viscous force proportional to the
square of the fluid velocity, F = −ρβ|u|u, on the right-hand side of Equation 7-52; see
References for the Darcy’s Law Interface for details.

In case of a flow with variable density, Equation 7-51 and Equation 7-52 must be
solved together with the equation of state that relates the density to the temperature
and pressure (for instance the ideal gas law).

For incompressible flow, the density stays constant in any fluid particle, which can be
expressed as

∂ ( ε ρ ) + u ⋅ ∇ρ = 0
∂t p

648 | CHAPTER 7: FLUID FLOW INTERFACES

and the continuity equation (Equation 7-51) reduces to

ρ∇ ⋅ u = Q m

References for the Brinkman Equations Interface

1. D. Nield and A. Bejan, Convection in Porous Media, 3rd ed., Springer, 2006.

2. M. Le Bars and M.G. Worster, “Interfacial Conditions Between a Pure Fluid and a
Porous Medium: Implications for Binary Alloy Solidification,” J. Fluid Mech.,
vol. 550, pp. 149–173, 2006.

THEORY FOR THE BRINKMAN EQUATIONS INTERFACE | 649

 Theory for the Coupling of Fluid
Flow to Electrochemical Reactions
Also see Theory for the Coupling of Mass Transport to Electrochemical Reactions for
how to calculate molar and mass fluxes, sources and sinks.

Momentum Sources and Sinks

The flow velocity, u (SI unit: m/s), at a boundary is coupled to the total mass flux of
the species at the electrode surface in the following way

1
u ⋅ n = ---
ρ  ni ⋅ n (7-53)
i

where ρ (SI unit: kg/m3) is the density of the flowing media, n the surface normal and
ni is the mass flux of species i.

For flow interfaces solving for the velocity field, no-slip conditions are applied at the
electrode surface, resulting in

1 
u = –  ---
ρ  Mi Ni n (7-54)
i

where Mi (SI unit: kg/mol) is the species mass and Ni (SI unit: mol/(m2·s)) the molar
flux calculated by Faraday’s law.

For a porous electrode the sum of all mass fluxes are added to the conservation
equation according to:

∂ρ
------ + ∇ ⋅ ( ρu ) =
∂t  Ri, mass (7-55)
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.

650 | CHAPTER 7: FLUID FLOW INTERFACES

 8

Heat Transfer

As with all other physical descriptions simulated by COMSOL Multiphysics, any

description of heat transfer can be directly coupled to any other physical process.
This is particularly relevant for systems based on chemical reactions and mass
transfer along with fluid flow. These physics interfaces are found under the Heat
Transfer branch ( ).

The basic functionality for simulating heat transfer in homogeneous media is

described in The Heat Transfer Interfaces in the COMSOL Multiphysics Reference
Manual.

The Battery Design 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 Battery Design Module irrespective of whether a separate Heat
Transfer Module license is purchased.

In this chapter:

• Coupling of Heat Transfer to Electrochemical Reactions

651
 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
• Heat of mixing

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

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

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

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

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

You can also use the heat source variables defined by the electrochemistry interfaces
when setting up manual heat couplings between different components in a model. For
instance if you are using a 1D electrochemical cell model to calculate an average heat
source in a 3D heat transfer model. The names of the heat source variables are 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

652 | CHAPTER 8: HEAT TRANSFER

Joule Heating Due to Charge Transport
As the charged particles are transported in an electric field, electrical energy is
converted into heat. The heat source terms for Joule heating in the electrode and
electrolyte phases are computed similarly by multiplying the current vector to the
gradient of the potential field variable according to

Q JH = – ( i s ⋅ ∇φ s + i l ⋅ ∇φ 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 Energy - Electrical Energy Generated

Using Faraday’s law for an electrode reaction, m, at the interface between the electron
and ion conducting phase this corresponds to

ΔH m ΔG m
Q m =  ------------- –  ------------- – η m, tot  i m (8-2)
 nm F  nm F 

where ΔHm is the enthalpy change of the reaction, and ΔGm is the Gibbs free energy
of the reaction, ΔGm, defined as

ΔG m = ΔH m – TΔS m

where ΔSm is the net entropy change. Equation 8-2 may now be rearranged into

TΔS m
Q m =  η m, tot + ---------------- i m (8-3)
 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 8-2 we have used the total overpotential, ηm,tot,(including potential

effects from film resistances and similar), defined as

η m, tot = φ s – φ l – E eq, m

The equilibrium potential is related to ΔGm in the following way:

COUPLING OF HEAT TRANSFER TO ELECTROCHEMICAL REACTIONS | 653

 ΔG m
E eq, m = – -------------
nm F

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

∂E eq, m ΔS m
------------------
- = -----------
-
∂T nm F

the local heat source due to the electrochemical conversion process becomes

∂E eq, m
Q m =  η m, tot + T ------------------- i m
 ∂T 

Alternatively, by defining the thermoneutral voltage of the reaction as

ΔH m
E therm, m = – -------------
nm F

one may also define the heat source as

Q m = ( η m, tot + ( E eq, m – E therm, m ) )i m

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

Q EC =  Qm
m

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

Q TOT, p =  av, m Qm + QJH

m

Heating Due to Heat of Mixing

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

654 | CHAPTER 8: HEAT TRANSFER

in the Electrochemistry interfaces, except for intercalating porous electrodes in the
battery interfaces (see next section).

Heat of Mixing in Intercalating Electrodes

For intercalating porous electrodes in the battery interfaces, the heat of mixing qmix,i
(W/m3) of a species of index i is defined as (see Ref. 3)

q mix, i = – J i ⋅ ∇H i

where Ji (mol/(m2s)) is the molar flux and Hi (J/mol) is the molar enthalpy.

This expression could be seen as a species transport version of Joule heating in an

electronic conductor, for which the heat source is defined as the current density
multiplied by the gradient of the potential.

Generally, for an intercalation material, two species are considered: the intercalated
species, denoted with index s, and the holes, denoted with index θ.

The flux of the two species are equal and opposite.

Js = –JΘ

We now define the total heat of mixing as the sum of the contributions from the two
species and write

q mix = q mix, s + q mix, Θ = – J s ⋅ ∇ ( H s – H Θ )

The absolute value of the individual molar enthalpies are generally not known.
However, the difference of the gradients of the molar enthalpies are related to the
thermoneutral voltage, Etherm (V) of the intercalation reaction.

The thermoneutral voltage is defined as

ΔH ( ΔG + TΔS ) dE eq
E therm = – --------- = – -------------------------------- = E eq – T -------------
F F dT

where ΔH is the change of molar enthalpy of the redox reaction.

In the case of lithium intercalation the redox reaction is

+ -
Li + e ⇔ Li(s)

with index s = Li(s) so that

COUPLING OF HEAT TRANSFER TO ELECTROCHEMICAL REACTIONS | 655

 ΔH = H Li(s) – H Li + – H θ

We now note that, if assuming the equilibrium potential to be independent of the

electrolyte lithium ion concentration,

dE eq, therm
∇ ( H s – H θ ) = – ∇ ( FE eq, therm ) = – F --------------------------- ∇c s
dc s

and finally we get

dE eq, therm
q mix = – J s ⋅  – F --------------------------- ∇c s
 dc s 

which is added to the expression for QTOT,p above.

Total Overpotential Calculation for Concentration Dependent

Kinetics
When using the Concentration Dependent kinetics option, in the Porous Electrode
Reaction and Electrode Reaction nodes, the equilibrium potential is typically a
constant referring to a reference state, and the concentration dependence of the
kinetics is accounted for only in the pre-exponential terms according to

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

where

η m = φ s – φ l – E eq, m

A result of this is that, when the pre-exponential factors CO,m and CR,m differ due to
concentration gradients, we at zero activation overpotential may have a net
charge-transfer current density flowing over the electrode-electrolyte interface. This
local current density obviously should give rise to a heat source. The solution is to add
a concentration overpotential term to the total overpotential when calculating the heat
sources.

When using the Concentration Dependent kinetics option, the overpotential, used in
the irreversible heat term above, is calculated as follows:

η m, tot = φ s – φ l – E eq, m + η m, conc

656 | CHAPTER 8: HEAT TRANSFER

where

RT C O, m
η m, conc = ------------ ln --------------
n m F C R, m

If the number of electrons is not available,

nm = α · + α c, m
a, m

is assumed.

References
1. Bernardi et al “A General Energy Balance for Battery Systems”, Journal of the
Electrochemical Society, 132 (1985), 5-12

2. Thomas et al “Thermal Modeling of Porous Insertion Electrodes”, Journal of the

Electrochemical Society, 150 (2003), A176-A192

3. Electrochemical Systems, Newman and Thomas-Alyea, Chapter 13 Thermal Effects

COUPLING OF HEAT TRANSFER TO ELECTROCHEMICAL REACTIONS | 657

658 | CHAPTER 8: HEAT TRANSFER
 9

Solid Mechanics

The Battery Design Module extends in the The Solid Mechanics Interface with
functionality for modeling strains occurring as a result of insertion of species
(atoms) into electrodes.

See the Intercalation Strain node in the COMSOL Multiphysics Reference

Manual.

659
660 | CHAPTER 9: SOLID MECHANICS
| 661
662 | CHAPTER 9: SOLID MECHANICS
 10

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

663
 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:

664 | CHAPTER 10: 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, for example, 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, that is, 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 | 665

 Thermodynamics
To access the functionality for thermodynamic calculations, right-click the Global
Definitions node in the Model Builder tree and select Thermodynamics ( ). When the
model includes a Component, Thermodynamics is also available on the Physics toolbar.

Using the Reaction Engineering or Chemistry interfaces, Thermodynamics is also

available on the Reaction Engineering or Chemistry toolbar.

Figure 10-1: The Thermodynamics is always 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 built-in database included with COMSOL Multiphysics.

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).

666 | CHAPTER 10: 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 the COMSOL database. You can also edit available species in the database.

Figure 10-2: 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 | 667

 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 10-3: 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. Using a formula, all species whose chemical
formula includes a combination of the given atoms are listed. For example, when
searching for ammonia NH3 or H3N can be used.

Select one or more species in the list and click the Add Selected button ( ) to add
species to the Selected species table. You can also press the Enter key to add either the

668 | CHAPTER 10: THERMODYNAMICS

first species in the list, or the species that have been selected. 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 10-4: 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 | 669

 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 thermal conductivity

670 | CHAPTER 10: 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 10-5: 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 | 671

 the text in the Label text field changes the name of the system. Below follows a
description of the thermodynamic system settings.

Figure 10-6: Thermodynamic System Settings.

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.

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.

672 | CHAPTER 10: THERMODYNAMICS

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 both gas and liquid phases are available, and the Liquid phase model is
set to an equation of state, then the Gas phase model is set to the same model
automatically.

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 10-7
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 10-7: Entering the Binary Interaction Parameters for the Soave–Redlich–Kwong
model.

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).

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 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 have been changed, select Update
From Species for the changes to take effect in the thermodynamic system.

Figure 10-8: 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.

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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. Thermodynamics in COMSOL
Multiphysics 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).

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 • Aspen Properties, aspenONE® (Aspen Technology, Inc.).
• COMThermo® packages (comes with Aspen HYSYS®).

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 more than 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 10-2). 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.

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SELECT PROPERTY PACKAGE
All installed packages, from providers such as COCO/TEA, Aspen Properties, and so
on, are available in the Thermodynamic System Wizard (Figure 10-9). 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 10-9: 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.

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 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.

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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 10-10: 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.

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 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 10-11: 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.

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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 10-12: 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.

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 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 10-8) 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 10-2). Use the Select File window to navigate to a thermodynamic system file
and click Open.

It is possible to manually modify the species properties, such as parameters and

temperature-dependent functions, in the created Thermodynamic System by using
Export Thermodynamic System and Import Thermodynamic System. In the saved xml file
from Export thermodynamic system, there are all parameters and
temperature-dependent properties for species, which 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">
• Find the line with the acentric factor and change it to
<AcentricFactor >0.2</AcentricFactor>.

682 | CHAPTER 10: THERMODYNAMICS

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 10-1: 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
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

USING THERMODYNAMIC PROPERTIES | 683

 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. The second-order derivatives with respect to temperature and pressure are
available for property functions of density and molar volume.

Right-click the relevant Thermodynamic System node (see Figure 10-8), 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.

684 | CHAPTER 10: THERMODYNAMICS

Click the Next button ( ) to proceed to the next step, selecting the phase.

Figure 10-13: Species Property Wizard; Select Properties.

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 10-14: Species Property Wizard; Select Phase.

Note that for parameters (constants) this step is skipped.

Click the Next button ( ) to proceed to the next step, selecting the species.

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.

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 Click the Next button ( ) to proceed to the Species Property Overview in the
wizard.

Figure 10-15: 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.

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 10-16: Create a Species Property from an existing species node.

686 | CHAPTER 10: THERMODYNAMICS

SETTINGS
Selecting a Species Property node shows the settings for such property.

Figure 10-17: 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.

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 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 10-18: 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 10-19: Properties window for species function.

688 | CHAPTER 10: THERMODYNAMICS

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. The second-order derivatives with respect to
temperature and pressure are available for property functions of density and molar
volume.

Right-click the relevant Thermodynamic System node (see Figure 10-8), 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

USING THERMODYNAMIC PROPERTIES | 689

 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.

MIXTURE PROPERTY OVERVIEW

The final step of the wizard displays an overview of the 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 10-20: 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.

690 | CHAPTER 10: THERMODYNAMICS

Equilibrium calculations involve combining the VLE-equations with material balances
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. Thermodynamics in
COMSOL Multiphysics 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 10-8), 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.

USING THERMODYNAMIC PROPERTIES | 691

 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.

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 10-21: 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

692 | CHAPTER 10: THERMODYNAMICS

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.

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 phenomenon 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 10-20).

SETTINGS
Selecting an Equilibrium Calculation node displays the settings including the property
functions, see Figure 10-22.

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 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 10-22: 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.

694 | CHAPTER 10: THERMODYNAMICS

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 in Chemistry. This means that the species name could be different in
Thermodynamics and Chemistry for a 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

USING THERMODYNAMIC PROPERTIES | 695

 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, viscosity and the
diffusivity. Two types of property functions can be used, either functions from the
underlying thermodynamics 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.

696 | CHAPTER 10: THERMODYNAMICS

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, (ρ)
• Diffusion coefficient at infinite dilution
• Heat capacity (Cp)
• Thermal conductivity (k)
• Viscosity (μ)

For a gas phase material, the Heat capacity ratio (γ = 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 ( )

USING THERMODYNAMIC PROPERTIES | 697

 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 10-23: 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 ∂ρ
α iso = – --- ------- (10-1)
ρ ∂T

For a gas phase material, the speed of sound c, and the isentropic compressibility χf are
also defined as

∂p 1 ∂ρ (10-2)
c= γ ------, χ f = ------ ------
∂ρ γρ ∂p

Click the Next button ( ) to proceed to the next step.

698 | CHAPTER 10: THERMODYNAMICS

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 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 are 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 functions. 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 and pressure ranges 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

USING THERMODYNAMIC PROPERTIES | 699

 define the number of 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.

The 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.

700 | CHAPTER 10: THERMODYNAMICS

REACTION ENGINEERING

Mixture Properties
You can couple a Reaction Engineering interface with an existing thermodynamic
system in the Reaction Engineering interface’s settings window.

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 10-24: 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.

USING THERMODYNAMIC PROPERTIES | 701

 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 10-25: Matching the species in Reaction Engineering to those in the corresponding
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 below.

Figure 10-26: 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.

702 | CHAPTER 10: THERMODYNAMICS

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.

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 10-27: 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 10-26.

USING THERMODYNAMIC PROPERTIES | 703

 MIXTURE PROPERTY DEFINITIONS WHEN COUPLING TO
THERMODYNAMICS
When all species in a physics interface (Reaction Engineering or Chemistry) 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 the temperature T, the
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 (10-3)
i=1

where Z i is the partial molar of species i:

∂Z mix ( T, P, n 1, n 2, …, n m )
Z i =  ----------------------------------------------------------------------- (10-4)
 ∂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 ) = (10-5)

 ∂Z mix ( T, P, x 1, …, x m )
Z +  ------------------------------------------------------------
 mix ( T, P, x 1, …, x m )  ∂xi  T, P, x
 i≠j


 x  ∂-----------------------------------------------------------
Z mix ( T, P, x 1, …, x m )
m

–   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 ) (10-6)
i=1

using the pure species properties Zi = Zmix(T, P, xi =1, 0, …, 0).

704 | CHAPTER 10: THERMODYNAMICS

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 10-28 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
thermodynamic system containing toluene, have been entered in the corresponding
input fields using the appropriate arguments.

Figure 10-28: 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

USING THERMODYNAMIC PROPERTIES | 705

 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
• 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

706 | CHAPTER 10: THERMODYNAMICS

2 Enter Parameters
3 Define Properties

ENTER NAME AND FORMULA

Enter the Name, CAS number, and the Chemical formula for the new species.

Figure 10-29: 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 10-30: 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.

USING THERMODYNAMIC PROPERTIES | 707

 Constants
Use this table to define material constants such as molar mass, critical temperature, and
standard enthalpy of formation.

Figure 10-31: 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 10-32: User-Defined Species Wizard; Specify the structure information in the
Enter Parameters step.

708 | CHAPTER 10: THERMODYNAMICS

Model parameters
Specify the parameters for the thermodynamic models and transport models in use.

Figure 10-33: 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 (10-7)

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).

USING THERMODYNAMIC PROPERTIES | 709

 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 10-34: 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 10-35 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).

710 | CHAPTER 10: THERMODYNAMICS

Figure 10-35: 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

USING THERMODYNAMIC PROPERTIES | 711

 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 ) (10-8)
RT

712 | CHAPTER 10: THERMODYNAMICS

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 comparison of different cubic
EOS models can be found in Ref. 2 and Ref. 3.

The equations 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 = -------- (10-9)
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. 5 is given by

RT aα
P = ------------- – ------------------------------------
- (10-10)
V – b V 2 + 2bV – b 2

where for species i,

2 2
R Tc
a i = Ω A -------------- (10-11)
Pc

RT c
b i = Ω B ----------- (10-12)
Pc

1 1
Ω A = --- + --- Ω B ( 4 + 10Ω B ) (10-13)
3 3

THERMODYNAMIC MODELS AND THEORY | 713

 Ω B =  β – ----------------- – 0.03125
63
(10-14)
1024β

1
---
3
β =  ---------------- + ------------- 2
351 27
(10-15)
32768 2048

The alpha function, αi, is given by

2
α i = [ 1 + ( 0.37464 +1.54226ω i – 0.26992ω i2 ) ( 1 – T r, i ) ] (10-16)

For mixtures

  xi xj ( 1 – kPR,i,j )
aα = ( aα ) i ( aα ) j (10-17)
i j

 xi bi
b = (10-18)
i

The binary interaction parameters (BIPs), kPR, are symmetric with zeros in the
diagonal:

k PR = k PR,i,j (10-19)

k PR,i,j = 0 (10-20)

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, ωi must be specified for all species.

Peng–Robinson (Twu)
For the Twu modification (Ref. 6) of the Peng–Robinson model, the alpha function,
αi, is replaced by

( Ni ( Mi – 1 ) ) NM
αi = T + R exp ( L i ( 1 – T r, ii i ) ) (10-21)

The binary interaction parameters kPR, are used for the Twu modification. Acentric
factor, ωi, 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.

714 | CHAPTER 10: THERMODYNAMICS

Soave–Redlich–Kwong
The classical Soave–Redlich–Kwong equation of state Ref. 7 is given by

RT aα
P = ------------- – ----------------------- (10-22)
V – b V(V + b)

with

1
α = -------- (10-23)
T

and for the pure species i,

2 2.5
R Tc
a i = Ω A ------------------ (10-24)
Pc

RT c
b i = Ω B ----------- (10-25)
Pc

1 1
Ω A = --- + --- Ω B ( 3 + 3Ω B ) (10-26)
3 3

1 2
--- ---
1 3 3 1
Ω B = ------ 2 27 – --- (10-27)
27 3

For mixtures

  xi xj ( 1 – kSRK,i,j )
a = ai aj (10-28)
i j

 xi bi
b = (10-29)
i

The binary interaction parameters, kSRK, are symmetric with zero in the diagonal:

k SRK ,i,j = k SRK ,j,i (10-30)

k SRK ,i,j = 0 (10-31)

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, ωi, must be specified for all species. The Soave–Redlich–Kwong equation of

THERMODYNAMIC MODELS AND THEORY | 715

 state is a version of Equation 10-22 modified by Soave Ref. 8, where for pure species
i, the alpha function is modified to

2
α i = [ 1 + ( 0.480 +1.574ω i – 0.176ω i2 ) ( 1 – T r, i ) ] (10-32)

Soave–Redlich–Kwong (Graboski–Daubert)
The Graboski and Daubert Ref. 9 modification of the Soave–Redlich–Kwong equation
of state replaces alpha function by

2
α i = [ 1 + ( 0.48508 +1.55174ω i – 0.1561ω i2 ) ( 1 – T r, i ) ] (10-33)

except for H2, where it is replaced by

α H2 = 1.202 exp ( – 0.30228T r, H 2 ) (10-34)

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. 10 - Ref. 12. The correlations are valid in the
following ranges:

273.15 K ≤ T ≤ 1073.15 K p ≤ 100 MPa (10-35)

1073.15 K ≤ T ≤ 2273.15 K p ≤ 50 MPa (10-36)

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 the COMSOL database.

LIQUID PHASE MODELS

Activity coefficient models

Activity coefficient models are used to describe liquid mixtures at low to moderate
pressures and temperatures where the equations of state are inadequate. When using
activity coefficient models, the partial fugacity for species i in the liquid phase is defined
as

716 | CHAPTER 10: THERMODYNAMICS

 f̂ i, l = x i γ i φ i, sat P i, sat F i (10-37)

which yields

P i, sat
φ̂ i, l = γ i φ i, sat ------------- F i (10-38)
P

where the activity coefficient, γi, describes the nonideal liquid phase and φ̂ 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 
(10-39)

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 ) (10-40)
 RT 

The Poynting correction can often be ignored for moderate pressure. Hence,
Equation 10-38 can be expressed as

P i, sat
φ̂ i, l = γ i φ i, sat ------------- (10-41)
P

If the vapor phase is considered ideal, then φ i, sat = 1 and the above equation reduces
to

P i, sat
φ̂ i, l = γ i ------------- (10-42)
P

This reduction can be selected explicitly in case the vapor phase is not ideal.

The logarithmic transformation of Equation 10-38 is:

ln φ̂ i, l = ln γ i + ln φ i, sat + ln P i, sat – ln P + ln F i (10-43)

Ideal Solution
For an ideal solution the activity coefficient is equal to one, which gives:

ln γ i = 0 (10-44)

THERMODYNAMIC MODELS AND THEORY | 717

 Regular Solution
The Scatchard–Hildebrand equation Ref. 14 for a nonpolar mixture is

2
V i ( δ i – δ av )
ln γ i = -------------------------------- (10-45)
RT

where Vi is species molar volume and δi is species solubility parameter, and δav is

 ( xi Vi δi ) (10-46)
i
δ av = ----------------------------
 ( 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, δi must be specified
for all species and can be estimated from the normal heat of vaporization, ΔHvap,i and
the liquid volume at normal boiling point as below:

ΔH vap, i
δ i ≡ ------------------- (10-47)
V i, l, b

Extended Regular Solution

The extended Scatchard–Hildebrand equation adds the Flory and Huggins correction
to the regular solution model Ref. 16:

2
V i ( δ i – δ av )
ln γ i = -------------------------------- + ln ( θ i ) + 1 – θ i (10-48)
RT

where

Vi
θ i = ----------------------- (10-49)
 ( xi Vi )
i

Wilson
Wilson Ref. 17 derived his activity coefficient model from a consideration of
probabilities of neighboring molecules in a liquid

718 | CHAPTER 10: THERMODYNAMICS

  
 xΛ 
 ------------------------ – ln 
, 
  xj Λi, j
j j i
ln γ i = 1 –   (10-50)

j
 
 x k Λ j, k

j
k

V w, j λ i, j
Λ i, j = ----------- exp  – -------- (10-51)
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 λi,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

λ i, i = 0 (10-52)

Λ i, i = 1 (10-53)

NRTL
Renon and Prausnitz (Ref. 18) formulated a three parameter activity coefficient model
that is able to describe liquid-liquid equilibrium; the nonrandom two-liquid (NRTL)
model:

  
 xj τj, i Gj, i 
 x j G j, i 
  x k τ k, j G k, j 
 (10-54)

j k
ln γ i = ------------------------------
-+  -------------------------  τ i, j – ----------------------------------
 x G  
 x j G j, i j   k k, j   x G
k k, j  
j  k  k 

A i, j
τ i, j = --------- (10-55)
T

G i, j = exp ( – α i, j τ i, j ) (10-56)

The three parameters are Ai,j, Aj,i, and αi,j. A more general form is implemented here:

A i, j
τ i, j = --------- + B i, j (10-57)
T

G i, j = exp ( β i, j – α i, j τ i, j ) (10-58)

THERMODYNAMIC MODELS AND THEORY | 719

 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.

The randomness parameters, αi,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 βi,j for which diagonal values are zero
and the matrix is nonsymmetric. For each pair of species at least αi,j or βi,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 (10-59)

B i, i = 0 (10-60)

α i, i = 0 (10-61)

α j, i = α i, j (10-62)

τ i, i = 0 (10-63)

G i, i = 1 (10-64)

β i, i = 0 (10-65)

UNIQUAC
Abrams and Prausnitz followed up with another two-liquid model known as Universal
Quasi Chemical equation (UNIQUAC) (see Ref. 19), which is formulated in terms of
two activity coefficients:

ln γ i = ln γ i, comb + ln γ i, res (10-66)

The first term is the combinatorial part contributes to the Gibbs free energy
originating from size and shape effects as

φi φi
ln γ i, comb = 1 – φ i + ln φ i – --- q i  1 + ---- + ln  ---- 
z
(10-67)
2  θi  θ i 

720 | CHAPTER 10: THERMODYNAMICS

and the second term is the residual part from chemical interactions between the
molecules,

   

  j

 x j q j τ j, i
 x j q j τ j, i 

ln γ i, res = q i  1 – ln  -------------------------
 
- –
 --------------------------- (10-68)
x j q j  x j q j τ k, j



 j 
j  
k

where

ri
φ i = ----------------- (10-69)
 xj rj
j

qi
θ i = ----------------- (10-70)
 xj qj
j

– Δ E i, j
τ i, j = exp  ----------------- (10-71)
 T 

The coordination number is taken equal to z = 10. The binary interaction energy
parameters, ΔEi,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.

ΔE i, i = 0 (10-72)

τ i, i = 1 (10-73)

The volume parameters, ri and surface area parameters, qi are model-specific

parameters for each species. If the parameters are not specified, they can be derived
from the van der Waals volume, VVDW,i, and area, AVDW,i, respectively

V VDW,i
r i = -------------------------------------
–3
- (10-74)
0.01517 ⋅ 10

A VDW,i
q i = ------------------------
–5
(10-75)
2.5 ⋅ 10

THERMODYNAMIC MODELS AND THEORY | 721

 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. 20) uses
the same equations as UNIQUAC but the parameters are constructed from group
contributions. The model can be used if UNIQUAC parameters are not available for
all species. The activity coefficients are calculated from Equation 10-66. The
combinatorial part follows from equation Equation 10-67, where

ri =  νk, i rk (10-76)
k

qi =  νk, i qk (10-77)
k

where rk and qk are the values for group k in species i, andνk,i is the number of
occurrences of group k in molecule. The residual term in Equation 10-66 is calculated
from a summation over functional groups:

ln γ i, res =  νk, i ( ln γk, res – ln γi, k, res ) (10-78)

k

The values for ln(γk,res) are calculated from the mixture containing all species at a
specified composition x. The values for ln(γi,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 τ l, k
 x l q l τ k, l 

ln γ k, res = q k  1 – ln  --------------------------
 
- –
 ----------------------------- (10-79)
x l q l 
 x l q l τ m, l



 l 
j  
m

where xl and xm are the compositions of functional group l and m in the mixture

 xi νm, i
i
x m = ----------------------------------- (10-80)
 
 
 x i ν k, i
 
i k

For the calculation of a pure species’ i residual activity we get:

722 | CHAPTER 10: THERMODYNAMICS

 ν m, i
x m = ----------------- (10-81)
 ν 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

A k, m
τ k, m = exp  – ------------- (10-82)
 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. 21 through Ref. 26), with added groups from Balslev and Abildskov
(Ref. 27) 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. 13 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 φ i, l = ln γ i + ln φ i, l, 0 (10-83)

The activity is based on the Scatchard–Hildebrand equation Ref. 14 and presented in

Equation 10-45 to Equation 10-47. Chao–Seader specific values for liquid volume, Vi
and solubility parameter, δi 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 10-80, at normal boiling point temperature.
If the Chao–Seader specific solubility parameter, δi, is not specified, the generic
solubility parameter is used.

The fugacity coefficient for pure species i is correlated as

log φ i, l, 0 = log φ i, l, 1 + ω i log φ i, l, 2 (10-84)

THERMODYNAMIC MODELS AND THEORY | 723

 A i, 1
log φ i, l, 1 = A i, 0 + ---------- + A i, 2 T r, i + A i, 3 T r2, i + A i, 4 T r3, i (10-85)
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

A i, 12
log φ 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 ) (10-86)
T r, i

A Chao–Seader specific acentric factor ωi 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. 15 and given in Table 10-2.
TABLE 10-2: 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

724 | CHAPTER 10: THERMODYNAMICS

The enthalpy, entropy and Gibbs free energy can be calculated from Equation 10-109
to Equation 10-118.

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
ρ l = ------ (10-87)
Vl

Using a cubic equation of state, the solution has 1, 2, or 3 different roots for the
volume. The liquid density is defined as the root producing the highest density, and
the vapor density as the root producing the lowest density.

Equation of State
When an equation of state is selected as the liquid phase model, the liquid volume is
by default set to be calculated using the same equation of state model. The other liquid
volume models; Ideal Mixture, COSTALD, and Rackett are also available.

Note, the vapor phase model and the liquid volume cannot use different equation of
state models.

Ideal Mixture
For an ideal mixture the liquid volume is computed from the pure species densities
(corresponding to the saturated liquid density):

xi
V l, m =  --------
ρ i, l
(10-88)
i

In this case the pure species densities corresponds to the saturated liquid density, which
is available as a temperature dependent correlation for all species in the built-in
database.

COSTALD
Hankinson and Thomson Ref. 28 presented the Corresponding States Liquid Density
(COSTALD) equation as

V -
------------ = V r, ref ( 1 – ωV r, δ ) (10-89)
V mix

THERMODYNAMIC MODELS AND THEORY | 725

 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 (10-90)

e + fT r + gT r2 + hT r3
V r, δ = ---------------------------------------------------- (10-91)
T r – 1.00001

1   
V mix = --- 
4  xi Vi + 3   xi Vi2 / 3   xi Vi1 / 3  (10-92)
i i i

 2
 
 x i T c, i V i

i
T c = ------------------------------------------ (10-93)
V mix

 -----
T
 T- T < Tc
Tr =  c (10-94)
1 T ≥ Tc


ω =  xi ωi (10-95)
i

where the volume, Vi and acentric factor, ωi 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> 0.3×10-3 m3/mol

2
V i = 5.385 V VDW, i – 5.1022VVDW 3
+ 79.524VVDW (10-96)
,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 (10-97)

If the COSTALD acentric factor, ωi is not specified, it can be set equal to the generic
acentric factor for species i. A critical temperature, Tc,i must be specified for all species.

The correlation parameter values are:

TABLE 10-3: REDUCED VOLUME CORRELATION PARAMETERS IN COSTALD.

a -1.52816 e -0.296123
b 1.43907 f 0.386914

726 | CHAPTER 10: THERMODYNAMICS

TABLE 10-3: REDUCED VOLUME CORRELATION PARAMETERS IN COSTALD.

c -0.81446 g -0.0427258
d 0.190454 h -0.0480645
Rackett
The Rackett equation Ref. 29 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:

 x i T c, i    ( 1 + ( 1 – Tr )2 ⁄ 7 )  
2

Vl =  R
  - 
---------------------------
( MW ) i P c, i   Z r, i


  xi ( MW )i (10-98)
i i i

Tc =  xi Tc, i (10-99)
i

 -----
T
 T- T < Tc
Tr =  c (10-100)
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 (10-101)

Selecting the Right Thermodynamic Model

Which thermodynamic model is the most appropriate depends on a number of things,
for example the nature of the properties to be used, the operational pressure and
temperature, and not least the availability of the required model parameters. One
general introduction to how to select thermodynamic models, as well as estimating
missing parameters and validating properties can be found in Ref. 77.

THERMODYNAMIC MODELS AND THEORY | 727

 Below is a decision tree that can be used as a guide for choosing the thermodynamic
model:

Figure 10-36: Decision tree to select thermodynamics model.

Species Property References

All references used for the included constants and temperature-dependent properties
are available in the database file. 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.

728 | CHAPTER 10: THERMODYNAMICS

Ideal Gas
The ideal gas law is independent of composition and determines V at given T and P.
Density can be calculated from

1
ρ = ---- (10-102)
V

The partial fugacity coefficients

ln φ̂ i = 0 (10-103)

The ideal gas enthalpy for mixture

 T 
 xi  Hi, ig, T T
H ig = + C P, i, ig dT (10-104)
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
(10-105)
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

G ig = H ig – TS ig (10-106)

Equation of State
The equation of state determines V at given x, T, and P. Density can be expressed as
Equation 10-102. The partial fugacity coefficients are derived from

P
ˆ
0  Vi – --------
1 RT
ln φ̂ i = -------- (10-107)
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:

THERMODYNAMIC MODELS AND THEORY | 729

 ∂ ln φ̂ i
H = H ig – RT 2  xi  -------------
∂T 
- (10-108)
i

∂ ln φ̂ i
S = S ig – R  xi  ln φ̂i + T -------------
∂T 
- (10-109)
i

G = G ig – RT  xi ln φ̂i (10-110)
i

Heat Capacity

Heat capacity at constant pressure is calculated from

∂H
C P =  -------- (10-111)
 ∂T  P,x

It is available when enthalpy is available. Heat capacity at constant volume is defined by

∂H
C v =  -------- (10-112)
 ∂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  -------  ------- (10-113)
∂T P,x ∂T v,x

were v is a function of T and P. A Taylor expansion of vat constant composition gives

∂V ∂V
Δv =  ------- ΔT +  ------- ΔP = 0 (10-114)
∂T P,x ∂P T,x

Rearranging equations above gives

∂V 2
T  -------
 ∂T P,x
C v = C P + ------------------------ (10-115)
 ∂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 10-113 express as

730 | CHAPTER 10: THERMODYNAMICS

 Cp – Cv = R (10-116)

Specific heat capacity ratio is defined as

Cp
ϒ = ------- (10-117)
Cv

Activity Coefficient Models

The enthalpy, entropy, and Gibbs free energy follow from the activity coefficients and
the ideal gas contributions in Equation 10-104 – Equation 10-106. 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 γ i
T
H =  xi  Hi, ig, T ref
+ T ref
C P, i, ig dT – ΔH i, vap – RT --------------
∂T
(10-118)
i
2 ∂ ln φ̂ 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 
- (10-119)
i
∂ ln γ i ∂ ln φ̂ i, sat ΔH i, vap
+ ln γ i + T -------------- + ln φ̂ i, sat + T ------------------------ + R ---------------------
∂T ∂T T 

 T 
G =  xi  Hi, ig, T ref
+ T ref
C P, i, ig dT – T  S i, ig, T ref +

(10-120)
i
T C P, i, ig  Pi, sat 
- dT + RT  ln x i + ln γ i + ln φ̂ i, sat + ln --------------
- 
 T ref
-----------------
T   P ref  

Note that if the vapor phase is ideal, then the saturated fugacity, φ i, sat , contribution
can be ignored.

Other Properties
Partial fugacity is calculated from

fˆi = x i φ̂ i P (10-121)

Internal energy is calculated from

THERMODYNAMIC MODELS AND THEORY | 731

 U = H – PV +  xi Ui, ig, ref (10-122)
i

where Ui,ig,ref is the enthalpy of an ideal gas to the species enthalpy at the selected
reference state.

Helmholtz energy is calculated from

A = U – TS = G – PV (10-123)

K-values for phases p and q are taken from

φ̂ i, q
K i, p, q = --------- (10-124)
φ̂ i, p

If only liquid phases are defined, the K-value calculation is reduced to

γ i, q
K i, p, q = --------- (10-125)
γ i, p

 xi Mi
M mix = (10-126)
i

Standard Enthalpy of Formation and Absolute Entropy Terms

Formation terms are not included in the enthalpy, entropy, or 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

ΔH reac, ref =  νi ( ΔHf, ref ) (10-127)

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 ΔHf, i, ref (10-128)

i

732 | CHAPTER 10: THERMODYNAMICS

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 (10-129)
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 10-129 and in consequence Gibbs free energy Equation 10-110 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.

If user needs the absolute value of entropy of formation, it is possible to estimate it by:

S i = ΔS f, i =  νj Sabs, j (10-130)
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 (10-131)

ΔS f, NH3 = 2S abs, NH3 – ( S abs, N2 + 3S abs, H2 ) (10-132)

The values from RHS of Equation 10-132 can be extracted from

COMSOLThermoDB. This value should be used in Equation 10-128 to estimate the
absolute value of Gibbs free energy of species.

THERMODYNAMIC MODELS AND THEORY | 733

 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

THERMAL CONDUCTIVITY

Vapor

Ideal

The thermal conductivity correlations is according to:

λv =  xi λi, v + Δλv, P (10-133)

i

The pressure correction Δλv,P is calculated from the method of Stiel and Thodos, see
Ref. 30, which is applicable for ρr<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
Δλ v, P = ----------------------------- A ( exp ( ( Bρ r ) + C ) ) (10-134)
MT c1 / 6 Z c5

734 | CHAPTER 10: THERMODYNAMICS

 ρ
ρ r = ----- (10-135)
ρc

1
ρ c = ------ (10-136)
Vc

The mixing rules are as suggested by Yorizane, see Ref. 31:

 x i  x j V c, i, j
Vc = (10-137)
i j

 x i  x j V c, i, j T c, i, j (10-138)
i j
T c = -----------------------------------------------------
-
Vc

 xi ωi
ω = (10-139)
i

Z c = 0.291 – 0.08ω (10-140)

RT c Z c
P c = ----------------- (10-141)
Vc

 xi Mi
M = (10-142)
i

where the binary constants are

1
V c, i, j = --- ( V c1,/i3 + V c1, /j3 ) 3 (10-143)
8

T c, i, j = T c, i T c, j (10-144)

The Stiel and Thodos coefficients are

TABLE 10-4: PRESSURE CORRECTION PARAMETERS.

A B C
ρr < 0.5 A1=2.702E8 B1=0.535 C1=-1
0.5 ≤ ρr < 2.0 A2=2.528E8 B2=0.670 C2=-1.069
ρr ≥ 2.0 A3=0.574E8 B3=1.155 C3= 2.016

THERMODYNAMIC MODELS AND THEORY | 735

 However, in order to ensure 0th-order continuity at ρr = 0.5 and ρr = 2.0, the
following coefficients for 0.5 ≤ ρr < 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 = – ------------------------------------------------------------------------------------------------------------------------------- (10-145)
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 = – ------------------------------------------------------------------------------------------------------------------------------- (10-146)
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 ωi must be specified for all species.

Kinetic Theory

Lindsay and Bromley (see Ref. 32) provided an equation for the interaction parameters
of the method of Wassiljewa (see Ref. 33) based on the kinetic theory, to provide
mixture thermal conductivity from pure species values

 
 xλ 
 --------------------- + Δλ
,

i i v
λv = (10-147)
  v, P
i
 
 x j φ i, j

j

2
 T + 3   
 --- T   9
 T +  --4- T b, i T b, j
η i, v  M j 3 / 4   2 b, i 
φ i, j
1 
= --- 1 + ---------- -------  ------------------------------   ---------------------------------------------- (10-148)
4 η j, v  M i   3   
 T +  --- T b, i 
3
  T +  --2- T b, j 
   2  

where the pressure correction Δλv,P is calculated from Equation 10-134. Both vapor
thermal conductivity correlation λi,v and the vapor viscosity correlation ηi,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 ωi must be
specified.

Water (IAPWS)

The International Association of the Properties of Water and Steam recommend an

equation Ref. 34 which is valid in the following range:

736 | CHAPTER 10: THERMODYNAMICS

 273.15 K ≤ T ≤ 773.15 K p ≤ 100 MPa (10-149)

773.15 K ≤ T ≤ 923.15 K p ≤ 70 MPa (10-150)

923.15 K ≤ T ≤ 1073.15 K p ≤ 40 MPa (10-151)

Liquid
The following mixture models are available for liquid thermal conductivity

Ideal

To calculate the mixture liquid thermal conductivity, λl,m, the values of pure liquid
thermal conductivity correlations are mixed ideally

 x i λ i, l
λ l, m = (10-152)
i

The pressure dependence is based on the work of Missenard (Ref. 51) where

λ l, m, P
----------------- = 1 + QP r0.7 (10-153)
λ l, m

where Q is correlated as

Q = -0.013693477 + 0.057427673T r + 0.001617831 ( T r ) ( ln P 1 ) (10-154)

and the following mixing rules are used

T
T r = ------ (10-155)
Tc

P
P r = ------ (10-156)
Pc

RT c Z c
P c = ----------------- (10-157)
Vc

 x i V c, i
Vc = (10-158)
i

 x i T c, i
Tc = (10-159)
i

THERMODYNAMIC MODELS AND THEORY | 737

  xi Zc, i
Zc = (10-160)
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
-----------
λ l2, m
=  --------
λ l, i
(10-161)
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. 52 and Ref. 53). The pressure dependence is introduced using Equation 10-153
through Equation 10-160. All values for critical temperatures, Tc,i, critical volumes,
Pc,i and critical compressibility factors, Zc,i must be specified for all spices i.

Local Composition

The local composition model by Rowley (Ref. 53) uses an ideal and excess
contribution

λ l, m = λ l, ideal + λ l, excess (10-162)

The ideal part is based on mass fractions

λ l, ideal =  ω i λ i, l (10-163)
i

xi Mi
ω i = -------------------- (10-164)
 xj Mj
j

The excess term is based on NRTL local concentrations

738 | CHAPTER 10: THERMODYNAMICS

   ω i ω j G j, i ( λ j, i – λ i, l )
i j
λ l, excess = ------------------------------------------------------------------
- (10-165)
ω j G j, i
j

where Gj,i follows from Equation 10-58. The binary interaction terms follow from

ω i ω i, i λ i, l + ω j ω j, j λ j, l
λ i, j = λ j, i = -------------------------------------------------------- (10-166)
ω i ω i, i + ω j ω j, j

which is symmetric, and on the diagonal,

λ i, i = λ i, l (10-167)

and

ω i, i = ω i ( ω i + ω j G j, i ) (10-168)

with ϖi is the composition in the binary mixture of species i and j and the local
composition is equi-molar

M i G j, i
ω i = -------------------------------------------------- (10-169)
M i G j, i + M j G i, j

All liquid thermal conductivity correlations must be specified. The pressure

dependence is introduced using Equation 10-153 – Equation 10-160. 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 αi,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 10-54 to Equation 10-65.

Local Composition (Modified)

Rowley (Ref. 52) adapted the local composition model by replacing the mixing rule in
Equation 10-166 by the following

M i ( ω i ω i, i )λ i, l + M j ( ω j ω j, j )λ j, l
λ i, j = λ j, i = ---------------------------------------------------------------------------------- (10-170)
M i ( ω i ω i, i ) + M j ( ω j ω j, j )

THERMODYNAMIC MODELS AND THEORY | 739

 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. 34 which is valid in the following range:

273.15 K ≤ T ≤ 773.15 K p ≤ 100 MPa (10-171)

773.15 K ≤ T ≤ 923.15 K p ≤ 70 MPa (10-172)

923.15 K ≤ T ≤ 1073.15 K p ≤ 40 MPa (10-173)

VISCOSITY

Vapor

Wilke

Wilke, see Ref. 35, based his method for mixture viscosity of the vapor phase on kinetic
theory:

 
 xη  (10-174)
 ---------------------
i i, v 
ηv =  
-

i
 
 x j ψ i, j

j

2
 η i, v M j 1 / 4
 1 + ----------  -------- 
 η j, v Mi 
ψ i, j = ------------------------------------------------------ (10-175)
Mi
8  1 + -------
 M j

The vapor viscosity correlation ηi,v must be available for all species. In addition, all
molecular weights Mi must be specified.

Brokaw

Brokaw (see Ref. 36) uses the same basic equation as Wilke (Equation 10-174).
However, Equation 10-175 is replaced by

740 | CHAPTER 10: THERMODYNAMICS

 η i, v
ψ i, j = S i, j A i, j ---------
- (10-176)
η j, v

and the interaction parameter is defined as

 
β i, j  RM i, j – RM i0.45 ,j


A i, j = -------------------- 1 + ----------------------------------------------------------------------------------------- (10-177)
RM i, j  1 + RM i0.45 
2 ( 1 + RM i, j ) + ------------------------------------------------
,j
 ( β i, j ) ( 1 + RM i, j )

where

 4M i M j  1 / 4 Mi
β i, j =  ----------------------------2 , RM i, j = ------- (10-178)
 ( Mi + M )  Mj
j

The vapor viscosity correlation, ηi,v must be available for all species i. In addition, all
molecular weights Mi must be specified. If Lennard–Jones energy εi (see Ref. 37)
Stockmayer’s polar parameter δs,i(Ref. 38 and Ref. 39) are specified for both species i
and j then

T 2- + 1 --- δ δ
1 + --------
ε i ε j 4 s, i s, j
S i, j = ---------------------------------------------------------------------------
- (10-179)
T 1 T 1
1 + ---- + --- δ s, i 1 + ---- + --- δ s, j
εi 4 εj 4

Otherwise,

S i, j = 1 (10-180)

Davidson

The Davidson method, see Ref. 40, requires fewer compound specific parameters than
Brokaw, while reported accuracy is almost as good, and in the case of H2, even
surpasses it. The Davidson model only requires molar masses and the viscosities of the
pure gases. The model is based on fluidity, which is defined to be the reciprocal
viscosity.

1
f = --- (10-181)
η

The fluidity of the mixture is then calculated as:

THERMODYNAMIC MODELS AND THEORY | 741

  yi yj 
  ------------------
A
f = - ⋅ E i, j (10-182)
μi μj 
i, j

where yi is the momentum fraction of species i, Ei,j is the momentum transfer

coefficient of the species pair i, j, and A is a empirical species independent parameter
set to 1/3. The momentum fraction is given by:

xi Mi
y i = ----------------------------- (10-183)
 ( xj Mj )
j

and the momentum transfer coefficient is taken as:

2 Mi Mj
E i, j = --------------------------- (10-184)
Mi + Mj

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
- --------------------------- ζ
Δη v, P =  ----------------------- (10-185)
 T c1 / 6   101325 2 / 3 

where ξ is calculated from the correlation of Jossi (Ref. 41), which is applicable for
ρr < 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
(ξ + 1) = 1.0230 + 0.23364ρ r + 0.58533 ρ r2 (10-186)

– 0.40758 ρ r3 + 0.093324 ρ r4

ρ
ρ r = ----- (10-187)
ρc

742 | CHAPTER 10: THERMODYNAMICS

 1
ρ c = ------ (10-188)
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 (10-189)
i i

Zc =  xi Zc, i , Mt =  xi Mi (10-190)
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, Brokaw, and Davidson mixture
models. The vapor viscosity follows from

η v = η v, Wilke + Δη v, P (10-191)

where ηv,Wilke is calculated from Equation 10-174.

Pedersen Corresponding States Model

The corresponding states viscosity model of Pedersen (Ref. 42 and Ref. 43) applies to
both vapor and liquid phases of hydrocarbon mixtures. The selected reference species
is CH4.

The CH4 viscosity is calculated from Ref. 44, modified by Pedersen and Fredenslund
(Ref. 45) to avoid issues below 91 K where CH4 becomes solid

η CH 4 = η CH 4, 0 + ρ CH 4 η CH , 1 + F 1 η CH , 2 + F 2 η CH , 3 (10-192)
4 4 4

where

H+1
F 1 = -------------- (10-193)
2

1–H
F 1 = -------------- (10-194)
2

exp ( ΔT ) – exp ( – ΔT )
H = ------------------------------------------------------------- (10-195)
exp ( ( ΔT ) + exp ( – ΔT ) )

ΔT = T – 91 K (T ∈ K) (10-196)

THERMODYNAMIC MODELS AND THEORY | 743

 Here, ρCH4 is used in g/cm3; for the mass-mole conversion of ρCH4, a molecular
weight of MCH4 = 16.042568 g/mol is used.

The dilute gas part is given by

–L1 L2 L3
η CH 4, 0 = ---------- + -----------
/
– ----------- (10-197)
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

2
η CH 4, 1 = L 10 – L 11  1.4 – ln ----------------
T
(10-198)
 168 K

The remainder is given by the empirical correlation

L 12   L 15 
η CH 4, 2 = exp  --------- – L 13  exp  ( 10 ρ CH 4 )  L 14 – ----------- + (10-199)
T    T 3 / 2
 ρ CH – ρ c, CH 4 L 17 L 18  
4 - ( ρ CH )  L 16 + --------
 ------------------------------------ - + ---------  – 1
ρ 4  T 2 
 c, CH 4  T  

The correction term for solid CH4

L 19   L 22 
η CH 4, 3 = exp  --------- – L 20  exp  ( 10 ρ CH 4 )  L 21 – ----------- (10-200)
 T    T 3 / 2
 ρ CH 4 – ρ c, CH 4 L 24 L 25  
+  ----------------------------------- ( ρ CH 4 )  L 23 + --------- + --------
-  – 1

 ρ c, CH 4  T T  2


with the values of the parameters L1 through L25 are listed in Table 10-5 below:
TABLE 10-5: 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
L3 1.472818·105 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

744 | CHAPTER 10: THERMODYNAMICS

TABLE 10-5: METHANE VISCOSITY NUMERICAL COEFFICIENTS.

L8 4.274152 L17 145.29023444

L9 0.08141531 L18 6127.6818706
Here, ρCH4 is used in g/cm ; the critical density is given by ρc,CH4 = 0.16284 g/cm3.
3

The following equation by McCarty (Ref. 46) is solved for the density of CH4

 N 5 N 6
P = N 1 ρ CH T + ρ CH
2
 – N 2 T + N 3 T – N 4 + ------- – ------2- (10-201)
4 4
 T T 
 N 9 N 10  – N T + N + –------------ N 13
+ ρ CH
3  N 7 T – N 8 + ------- – ---------- + ρ CH 4
4
- + N 14 ρ CH 5
4
 T 2
T 
11 12 T  4

 N 15 N 16 ρ CH7
4  N 18 N 19 ρ CH9
4
+ ρ CH
6
 – ---------- + ---------
- + N 17 ------------- + ρ CH
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 ρ CH
2 )  ρ CH  ---------
2
- – ---------- + ρ CH
3
5  ---------
2
- + ---------- + ρ 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 
+ ρ CH
9
 – ---------
2
- – ---------- + ρ CH
4
11  – ---------
2
- + ---------- + ρ CH
3
13
 ---------
2
- – ---------- + N 34 T  
3
4
 T T 
4
 T T 
4
T T 

where ρCH4 is used in mol/l.

TABLE 10-6: 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
N5 848.44027562 N17 0.24986828379·10-4 N29 31.630780767
-5
N6 42738.409106 N18 0.57974531455·10 N30 0.4100678294·10-5
-3
N7 0.76565285254·10 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
-4 6
N11 0.37521074532·10 N23 1.4800512328·10
N12 0.028616309259 N24 50.498054887

With the viscosity and density of CH4 defined, the viscosity of any mixture, ηm, can be
calculated from the corresponding states principle

THERMODYNAMIC MODELS AND THEORY | 745

 –1
T c ------ Pc 2 / 3 Mm 1 / 2 α
η m =  ----------------- 6  -----------------  ---------------  ------------- η CH 4, P 0, T 0 (10-202)
 T c, CH   P c, CH   M CH   α CH 
4 4 4 4

where the CH4 viscosity ρCH4,P0,T0 is calculated at temperature T0 and pressure P0:

T c, CH α CH
T 0 =  ------------------4 T  -------------4 (10-203)
 Tc   α 

P c, CH α CH
P 0 =  -----------------4 P  -------------4 (10-204)
Pc α

The following mixing rules are used for the critical properties, see Ref. 47:

  x i x j β i, j T c, i T c, j
(10-205)
i j
-----------------------------------------------------------
-
Tc =
  x i x j β i, j
i j

8   x i x j β i, j T c, i T c, j
(10-206)
i j
P c = --------------------------------------------------------------
-
 2

  x i x j β i, j

i j

T c, i 1 / 3  T c, j 1 / 3 3
β i, j =   ---------- +  ----------  (10-207)
P c, i P c, j

The parameter α is

–3 0.5173
α = 1 + 7.378 ×10 ρ r1.847 M m (10-208)

ρ
CH 4, P 0, T 0
ρ r = --------------------------
- (10-209)
ρ c, CH 4

where

T c, CH
T 0 =  -----------------4 T (10-210)
 Tc 

746 | CHAPTER 10: THERMODYNAMICS

 P c, CH
P 0 =  -----------------4 P (10-211)
 Pc 

with ρc,CH4 = 0.16284 g/cm3. For CH4

–3 0.5173
α CH 4 = 1 + 7.378 ×10 ρ r1.847 M CH 4 (10-212)

where Equation 10-209 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 (10-213)

 xi Mi
2

i (10-214)
M W = --------------------
-
MN

 xi Mi
MN = (10-215)
i

where the power in Equation 10-213 is determined by fitting to experimental viscosity

data.

Note that pure species vapor viscosity correlations ηi,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. 48–Ref. 49 for industrial application which is valid in the following
range:

273.16 K ≤ T ≤ 1173.15 K 0 ≤ p ≤ pt (10-216)

T m ( p ) ≤ T ≤ 1173.15 K p t ≤ p ≤ 300 MPa (10-217)

T m ( p ) ≤ T ≤ 873.15 K 300 MPa ≤ p ≤ 350 MPa (10-218)

T m ( p ) ≤ T ≤ 433.15 K 350 MPa ≤ p ≤ 500 MPa (10-219)

T m ( p ) ≤ T ≤ 373.15 K 500 MPa ≤ p ≤ 1000 MPa (10-220)

THERMODYNAMIC MODELS AND THEORY | 747

 where Tm is the pressure dependent melting temperature and pt 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.

Molar Logarithmic Mixing

The values of pure species log liquid viscosity, ln ηi,l are mixed ideally using mole
fractions xi

ln η l, m =  xi ln ηi, l (10-221)
i

where ηm,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 ωi

ln η l, m =  ωi ln ηi, l (10-222)
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
η l, m = 
  x i η i1, /l3

(10-223)
i

The model is noted in Ref. 50 to provide reasonable results for hydrocarbon mixtures
of similar components.

748 | CHAPTER 10: THERMODYNAMICS

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
η l, m = 
  ω i η i1, /l3

(10-224)
i

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. 48–Ref. 49 for industrial application which is valid in the following
range:

273.16K ≤ T ≤ 1173.15K 0 ≤ p ≤ pt (10-225)

T m ( p ) ≤ T ≤ 1173.15 K p t ≤ p ≤ 300 MPa (10-226)

T m ( p ) ≤ T ≤ 873.15 K 300 MPa ≤ p ≤ 350 MPa (10-227)

T m ( p ) ≤ T ≤ 433.15 K 350 MPa ≤ p ≤ 500 MPa (10-228)

T m ( p ) ≤ T ≤ 373.15 K 500 MPa ≤ p ≤ 1000 MPa (10-229)

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. 54–Ref. 57). This

THERMODYNAMIC MODELS AND THEORY | 749

 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.

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

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 and others (Ref. 58) 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
- (10-230)
 --- ---
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. 59):
TABLE 10-7: 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

750 | CHAPTER 10: THERMODYNAMICS

TABLE 10-7: ATOMIC AND STRUCTURAL DIFFUSION VOLUME INCREMENTS

GROUP CONTRIBUTION

I 29.8
S 22.9
Aromatic Ring -18.3
Heterocyclic Ring -18.3

For some simple molecules the values below, determined from regression, are used:
TABLE 10-8: 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. 60) also modified the Chapman–Enskog relation to correlate
binary diffusion coefficient in vapor phase according to:

THERMODYNAMIC MODELS AND THEORY | 751

 3.03 –  --------------------- T
0.98 1.5
 MW 
0 –2 i, j
D i, j = 10 × -------------------------------------------------------
2
- (10-231)
Pσ i, j Ω D MW i, j

where

2
MW i, j = --------------------- (10-232)
1
------- + ------1-
Mi Mj

The length scale σ i, j for the interaction is taken from the Lennard–Jones diameter
parameters of species i and j:

LJ LJ
( σi + σj )
σ i, j = ------------------------------- (10-233)
2
LJ
If σ i is not specified in the database, it is instead estimated from:

--1-
LJ –8 3
σi = 1.18 × 10 V i, l, b (10-234)

where Vi,l,b is the molar volume of species at normal boiling point.

The collision integral ΩD is evaluated from (Ref. 61):

-0.15610
Ω D = 1.06036 T∗ + 0.19300 exp ( -0.47635 T∗ ) (10-235)
+ 1.03587 exp ( -1.52996 T∗ ) + 1.76474 exp ( -3.89411 T∗ )

with

T
T∗ = -------- (10-236)
ε i, j

The energy scale εi,j for the interaction is taken from the Lennard–Jones energy
parameters of species i and j:

LJ LJ
ε i, j = εi εj (10-237)
LJ
If ε i is not specified in the database, it is instead estimated from:

LJ
εi
--------
- = 1.15T i, l, b (10-238)
k

752 | CHAPTER 10: THERMODYNAMICS

where k is the Boltzmann constant and Ti,l,b is the 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

0
D i, j = D i, j (i ≠ j) (10-239)

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 ηj 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.

THERMODYNAMIC MODELS AND THEORY | 753

 • 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.
• 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 other 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. 62) for liquid phase diffusion coefficients at
infinite dilution is:

0 – 18 T φj Mj
D i, j = 1.858795959 × 10 --------------------
- (10-240)
0.6
η j V i, l, b

Molecular weight, Mj and log liquid viscosity correlation, ln η 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 φ j , if unavailable, is set to:
TABLE 10-9: ASSOCIATION PARAMETERS FOR SOLVENT

SOLVENT ASSOCIATION
PARAMETER

Water 2.26 (Ref. 63)

Methanol 1.9
Ethanol 1.5
Others 1

754 | CHAPTER 10: THERMODYNAMICS

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. 64) is applied where liquid molar volume of water at
normal boiling point, Vwater,l,b is multiplied by 4.5.

Tyn–Calus

The Correlation by Tyn and Calus (Ref. 65) 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 ------------------------------------- (10-241)
1
 --3-  0.6
η j  V j, l, b P i
 

The log liquid viscosity correlation ln ηj 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
normal boiling point, Vj,l,b and the parachor, Pj are corrected by a factor of 8 × 103ηj.

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. 66) 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:

THERMODYNAMIC MODELS AND THEORY | 755

 0 – 12 1.52  0.07244359601 
D i, j = 1.25 × 10 T  ----------------------------------------- - – 0.292 (10-242)
 0.19
V i, l, b 
× 10
–6
 9.58
---------------------------- – 1.12
3  V i , l, b 
× ( η j × 10 )

Normal paraffin solutions: In case both the solute and solvent are normal paraffins
(derived from SMILES formula), the correlation reads:

10.2 × 10
–6
 ---------------------------- – 0.791
  
 ( η × 10 3 ) V i, l, b 
– 16 1.47  j
---------------------------------------------------------------------
0
D i, j = 7.30889362 × 10 T (10-243)
 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 ---------------------------------------------
- (10-244)
0.92 0.23 0.42
η 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 η 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. 67) 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 --------------------------------------- (10-245)
1.026 0.5473
ηj ( V i, l, b )

For all other systems, the equation for organic solution is used as:

756 | CHAPTER 10: THERMODYNAMICS

 0.265
0 – 15 T ( V j, l, b )
D i, j = 1.459473761 × 10 ----------------------------------
- (10-246)
0.907 0.45
ηj ( V i, l, b )

Where T is the temperature, Vi,l,b is the liquid volume at normal boiling point and ηj
is the viscosity of the solvent.

Erkey–Rodden–Akgerman

The correlation by Erkey and others (Ref. 68) 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 ------------------------------------------------------------------------------------ (10-247)
0.239 0.781 – 20 1.134
Mi Mj ( σ i σ j × 10 )

where the reference volume is

ref 1 3
Vj = ------- b j N Av σ j (10-248)
2

NAv is Avogadro’s number, and the deviation from closest packing volume is given by

σi
b j = 1.206 + 0.0632  ----- (10-249)
σj

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, σi is estimated from Bondi
group contribution method (Ref. 69), and for some species are taken from Ref. 68 and
Ref. 70 as:
TABLE 10-10: MOLECULAR DIAMETERS FOR SPECIES
10
SPECIES σ × 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.

THERMODYNAMIC MODELS AND THEORY | 757

 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. 71) model for diffusion in binary solutions can be
extended to multi-component systems (Ref. 72):

n
xk
D i, j = ∏ (Di, j, x → 1 )k
(10-250)
k=1

where D i, j, x k → 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. 57) becomes unity and the Maxwell–Stefan diffusivity equals to
Fick diffusivity:

0 0
D i, j, xj → 1 = D i, j = D i, j (10-251)

Similarly,

0 0
D i, j, x i → 1 = D j, i = D j, i (10-252)

Models for the D i, j, xk → 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 (10-253)

and to ensure continuity if both species i and j vanish:

lim D i, j, xk → 1 = lim D i, j, xk → 1 (10-254)

xi → 0 xj → 0

For binary systems, Equation 10-250 reduces to the Vignes interpolation formula.

Wesselingh–Krishna

Wesselingh and Krishna (Ref. 72) proposed:

0 0
D i, j, x k → 1 = D i, j D j, i (10-255)

leading to:

758 | CHAPTER 10: THERMODYNAMICS

 0 ( 1 + xj – xi ) ⁄ 2 0 ( 1 + xi – xj ) ⁄ 2
D i, j = ( D i, j ) ( D j, i ) (10-256)

Kooijman–Taylor

Kooijman and Taylor (Ref. 73) 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 ) (10-257)

leading to:

n
0 xj 0 xi xk
∏(
0 0
D i, j = ( D i, j ) ( D j, i ) D i, k D j, k ) (10-258)
k = 1
k ≠ i, j

Wesselingh and Bollen (Ref. 74) asserted that this is a reasonable estimate.

Krishna–van Baten

Krishna and van Baten (Ref. 75), on the basis of data obtained from molecular
dynamic simulations, proposed the following Vignes-based (Ref. 71) 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 ) (10-259)

The model reduces to the Kooijman–Taylor model for xi = xj. The value of D i, j, x k → 1
is undefined in the limit of both xi → 0 and xj → 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 + εx 
 ----------------------------- xj + εx 
 -----------------------------
 x i + x j + 2ε x  x i + x j + 2ε x
0 0
D i, j, xk → 1 = ( D i, k ) ( D j, k ) ( k ≠ i, j ) (10-260)

where εx = 10−10 is taken as a small composition. The limiting case for both xi → 0 and
xj → 0 also reduces to the Kooijman–Taylor model. This equation leads to:

THERMODYNAMIC MODELS AND THEORY | 759

 n xi + εx
 ----------------------------- xj + εx
 ----------------------------- xk
  x + x + 2ε x  x i + x j + 2ε x 
0 xj 0 xi  ( D0 ) i j 
∏
0
D i, j = ( D i, j ) ( D j, i ) ( D ) (10-261)
 i , k j , k 
k = 1 
k ≠ i, j

Surface Tension
Below the available surface tension models are presented.

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 σi, vl
σ vl = (10-262)
i

where the vapor-liquid surface tension correlations, σi,vl, must be specified for all
species i, and are evaluated at the temperature of the liquid phase.

Winterfeld
Following Winterfeld (Ref. 76), the vapor-liquid surface tension is predicted by mixing
the pure species correlations according to

x i, l x j, l σ i, vl σ j, vl
  ---------------------------------------------
ρ i, l ρ j, l
-
i j
σ vl = -------------------------------------------------------------
- (10-263)
 x i, l  2

 --------
 ρ 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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Interior, Bureau of Mines, 1993.

41. J.A. Jossi, L.I. Stiel, and G. Thodos, “The viscosity of pure substances in the dense
gaseous and liquid phases,” AIChE Journal, vol. 8, no. 1, pp. 59–63, 1962.

42. K.S. Pedersen and P.L. Christensen, “Phase Behavior of Petroleum Reservoir
Fluids,” CRC Press/Taylor & Francis Group, 2007.

43. K.S. Pedersen, A. Fredenslund, P.L. Christensen, and P. Thomassen, “Viscosity of

crude oils,” Chemical Engineering Science, vol. 39, no. 6, pp. 1011–1016, 1984.

44. H.J.M. Hanley, W.M. Haynes, and R.D. McCarty, “The viscosity and thermal
conductivity coefficients for dense gaseous and liquid methane,” Journal of Physical
Chemistry, vol. 6, no. 2, pp. 597–609, 1977.

45. K.S. Pedersen and A. Fredenslund, “An improved corresponding states model for
the prediction of oil and gas viscosities and thermal conductivities,” Chemical
Engineering Science, vol. 42, no. 1, pp. 182–186, 1987.

46. R.D. McCarty, “A modified Benedict-Webb-Rubin equation of state for methane

using recent experimental data,” Cryogenics, pp. 276–280, May 1974.

47. S. Murad and K.E. Gubbins, “Corresponding states correlation for thermal
conductivity of dense fluids,” Chemical Engineering Science, vol. 32, no. 5, pp. 499–
505, 1977.

48. 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.

764 | CHAPTER 10: THERMODYNAMICS

49. 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.

50. J. Gabitto and M. Barrufet, “Experimental and theoretical determination of heavy

oil viscosity under reservoir conditions,” Technical reports, Office of Fossil Energy,
USDOE Office of Fossil Energy, United States, 2002.

51. 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).

52. 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.

53. R.L. Rowley, “A local composition model for multicomponent liquid mixture
thermal conductivities,” Chemical Engineering Science, vol. 37, no. 6, pp. 897–904,
1982.

54. W.D. Niven, “The Scientific Papers of James Clerk Maxwell”, Cambridge
University Press, 1890.

55. J.C. Maxwell, “On the dynamical theory of gases,” Philosophical Transactions of
the Royal Society of London, vol. 157, pp. 49–88, 1867.

56. 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.

57. R. Taylor and R. Krishna, “Multicomponent Mass Transfer,” Wiley-Interscience,

1993.

58. 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.

59. 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.

60. 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.

THERMODYNAMIC MODELS AND THEORY | 765

 61. P.D. Neufeld, A.R. Janzen, and R.A. Aziz, “Empirical equations to calculate 16 of
( l, s )∗
the transport collision integrals Ω for the Lennard–Jones (12-6) potential,” The
Journal of Chemical Physics, vol. 57, pp. 1100–1102, 1972.

62. C.R. Wilke and P. Chang, “Correlation of diffusion coefficients in dilute

solutions,” AICHE Journal, vol. 1, no. 2, pp. 264–270, 1972.

63. 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.

64. 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.

65. 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.

66. 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.

67. 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.

68. 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.

69. A. Bondi, “van der Waals Volumes and Radii”, Journal of Physical Chemistry,
vol. 68, no. 3, pp. 441-451, 1964.

70. J.O. Hirschfelder, C.F. Curtiss and R.B. Bird, “The Molecular Theory of Gases
and Liquids”, Wiley-Interscience, 1964.

71. A. Vignes, “Diffusion in Binary Solutions,” Industrial and Engineering

Chemistry Fundamentals, vol. 5, pp. 189–199, 1966.

72. J.A. Wesselingh and R. Krishna, “Mass Transfer”, Ellis Horwood Ltd, 1990,
ISBN: 0-13-553165-9.

73. H.A. Kooijman and R. Taylor, “Estimation of diffusion coefficients in

multicomponent liquid systems”, Industrial and Engineering Chemistry Research,
vol. 30, pp. 1217–1222, 1991.

766 | CHAPTER 10: THERMODYNAMICS

74. J.A. Wesselingh and A.M. Bollen, “Multicomponent diffusivities from the free
volume theory”, Chemical Engineering Research and Design, 75(6):590–602,
1997.

75. R. Krishna and J.M. van Baten, “The Darken relation for multicomponent
diffusion in liquid mixtures of linear alkanes: An investigation using molecular
dynamics (MD) simulations,” Industrial and Engineering Chemistry Research,
vol. 44, pp. 6939–6947, 2005.

76. P.H. Winterfeld, L.E. Scriven, and H.T. Davis, “An approximate theory of
interfacial tension of multicomponent systems: Applications binary liquid-vapor
tensions,” AIChE Journal, vol. 24, no. 6, pp. 1010–1014, 1978

77. E.C. Carlson, “Don’t Gamble With Physical Properties For Simulation”,
Chemical Engineering Progress, vol. 92, no. 10, pp. 35–46, 1996.

THERMODYNAMIC MODELS AND THEORY | 767

768 | CHAPTER 10: THERMODYNAMICS
 11

Multiphysics Coupling Nodes

The Battery Design 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.

769
 In this chapter, the following multiphysics couplings nodes are described:

• Deforming Electrode Surface • Space Charge Density Coupling

• Nondeforming Boundary
• Electrochemical Heating
• Potential Coupling

Deforming Electrode Surface

Use the Deforming Electrode Surface multiphysics coupling to model deformation of the
geometry due to an electrochemical deposition-dissolution process.

The node uses the deposition-dissolution velocity of an Electrode Surface boundary in

an Electrochemistry interface to apply a deformation velocity on to a deforming
boundary.

Special conditions for the tangential velocity at points (2D) and edges (3D) shared
with nondeforming surfaces apply, as described in the theory section.

The node, available as a multiphysics coupling node, is only applicable when both the
Electrochemistry interface (Primary/Secondary/Tertiary Current Distribution or
Lithium-Ion Battery or Battery with Binary Electrolyte) and a Deformed Geometry
node are added to a component.

MOVING BOUNDARY SMOOTHING

Certain electrode deformation problems are inherently unstable. The Moving
Boundary Smoothing will stabilize the moving boundary by applying a fictitious
surface tension. Use the Moving boundary smoothing tuning parameter, δmbs, to control
smoothing. A higher value means more smoothing.

RECOMMENDED SETTINGS IN THE COUPLED DEFORMED GEOMETRY

INTERFACE
Predefined multiphysics interfaces are available from the model wizard that will
automatically add and set up the coupling between a current distribution interface and
the deformed geometry node. However, you can also add a Deformed Geometry
interface manually to an already existing model.

The following settings are recommended in the Deformed Geometry interface if you
are manually setting up the coupling between a Deformed Geometry interface and an

770 | CHAPTER 11: MULTIPHYSICS COUPLING NODES

Electrochemistry interface using the Deforming Electrode Surface and Nondeforming
Boundary multiphysics coupling nodes:

• At the Deformed Geometry interface node, change the Geometry shape order to 1
and Mesh smoothing type to Hyperelastic
• Clear all the check boxes at the default Prescribed Mesh Displacement boundary
feature node
• Add Free Deformation domain node and make sure it is selected on the deforming
domains of the geometry

Tangential Velocities at the Intersection Between a Depositing and a

Nondepositing Boundary

Nondeforming Boundary
Use the Nondeforming Boundary multiphysics coupling to define boundaries that do not
undergo deformation in the normal direction.

A Nondeforming Boundary can be applied to external boundaries of an electrolyte and

is typically used to specify an insulator, a nondissolving/depositing electrode surface
or a symmetry boundary in a problem.

The node, available as a multiphysics coupling node, is only applicable when both the
Electrochemistry interface (Primary/Secondary/Tertiary Current Distribution or
Lithium-Ion Battery or Battery with Binary Electrolyte) and a Deformed Geometry
node are added to a component.

Zero normal displacement is implemented using pointwise constraints, which may be

more numerically stable, but should typically only be used for planar boundaries since
the boundary is effectively fixed in the tangential direction if the curvature of the
boundary is nonzero.

As a rule of thumb: use Zero normal displacement for planar boundaries and Zero normal
velocity for curved boundaries.

For 3D components, and when Zero normal displacement is selected, the deformation
may be further stabilized by enabling the Allow deformation along specified line only.
The specified line must be parallel to the boundary in the nondeformed geometry.

See also the Deforming Electrode Surface node.

| 771
 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.

772 | CHAPTER 11: MULTIPHYSICS COUPLING NODES

 12

Parameter Estimation

Battery models many times contain unknown parameters, for instance diffusion
constants or rate constants, that are hard to measure in separate experiments
outside (ex-situ) a battery cell. To fit model parameter values to experimental data,
the Parameter Estimation ( ) node, which may be added to a Study ( ) node in
the model builder tree, can be used.

The Battery Design Module includes the Parameter Estimation node, together
with the BOBYQA, IPOPT, and Levenberg–Marquardt optimization solvers,
which may be used to perform parameter fitting of both stationary and
time-dependent models.

The documentation of the parameter estimation node and the optimization solvers
is found in the Optimization Module User’s Guide, which is supplied with the
Battery Design Module irrespective of whether a separate Optimization Module
license is purchased.

• Parameter Estimation of a Time-Dependent Lumped

Battery Model: Application Library path
Battery_Design_Module/Batteries,_Lithium-Ion/
lumped_li_battery_parameter_estimation

773
774 | CHAPTER 12: PARAMETER ESTIMATION
 13

Glossary

This Glossary of Terms contains application-specific terms used in the Battery

Design 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.

775
 Glossary of Terms
anode An electrode where oxidation occurs. Anodic charge transfer current densities
and overpotentials are positive by definition. The negative electrode of a battery is
commonly referred to as “anode”, although this is strictly correct during discharge
only.

cathode An electrode where reduction occurs. Cathodic charge transfer current

densities and overpotentials are negative by definition. The positive electrode of a
battery is commonly referred to as “cathode”, although this is strictly correct during
discharge only.

cell voltage The difference in potential over an electrochemical cell.

charge transfer reaction A reaction during which charge is transferred from an

electron conducting phase (electrode) to an ion conducting phase (electrolyte).

charge transfer current density The current density at an electrolyte-electrode

interface associated with a charge transfer reaction.

concentrated electrolyte An electrolyte where the concentration of charged species is

so high that the interactions (friction forces) between the ions needs to be considered.
See also diluted electrolyte.

current collector A part of an electrochemical device with high electric conductivity

for conducting current out of the cell. See also current feeder.

current feeder A part of an electrochemical device with high electric conductivity for
conducting current into the cell. See also current collector.

diluted electrolyte An electrolyte where the charged species are diluted in a solvent so
that the interaction between the ions can be neglected. See also concentrated
electrolyte.

electric potential The potential in the electrode (electron conducting) phase, denoted
φs (phis).

electrode An electron conductor.

776 | CHAPTER 13: GLOSSARY

electrode reaction See charge transfer reaction.

electrokinetic flow Transport of fluid or charged particles within a fluid by means of

electric fields.

electrolyte An ion conductor.

electrolyte potential The potential in the electrolyte (ionic) phase, denoted φl (phil).

electroneutrality A situation where the net charge of any small control volume of a
domain is zero. Electroneutrality can usually be assumed for electrolytes, with an
exception for the very proximity of the electrolyte-electrode interface, which is due to
the charge separation within the electrochemical double layer.

equilibrium potential The potential difference between the electrode and electrolyte
at which the net current density of an electrode reaction is zero.

Faraday’s Law A mathematical expression relating the flux of a species over an

electrode-electrolyte interphase to be proportional to the charge transfer current
density.

gas diffusion electrode (GDE) A porous electrode that also includes gas pores in the
porous matrix.

GDE See gas diffusion electrode (GDE).

Gibbs free energy A thermodynamic potential that depends on the enthalpy and
entropy of the reacting species.

intrinsic volume averages The physical properties of the fluid, such as density,
viscosity, and pressure.

intercalation The process of ions reacting on the surface of a host particle to form a
solid, intercalated, species within the host. The intercalated species can then be
transported further into the particle by diffusion processes.

migration The transport of charged species in an electrolyte due to the electric force
imposed by the electric field.

morphology correction parameter A correction parameter that is used to account for

morphology effects of a porous structure.

GLOSSARY OF TERMS | 777

 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
COMSOL Multiphysics using the Tertiary Current Distribution, Nernst–Planck
interface (and the Transport of Diluted Species interface). The Nernst–Planck
equation is often combined with an electroneutrality condition.

Nernst–Planck–Poisson equation In certain situations, for instance when striving to

resolve the electrochemical double layer at an electrode, and electroneutrality cannot
be assumed, the Nernst–Planck equation is combined with the Poisson’s equation for
describing the charge density.

overpotential A deviation from the equilibrium potential.

oxidation A charge transfer reaction where electrons are produced.

PEMFC An abbreviation for proton exchange membrane fuel cell.

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.

778 | CHAPTER 13: GLOSSARY

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.

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.

Soret effect Mass diffusion in multicomponent mixtures due to temperature

gradients.

SOFC An abbreviation for solid oxide fuel cell.

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

GLOSSARY OF TERMS | 779

 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.

transport number The amount of the current that is transported by one of the species
in a binary electrolyte. Also called the transference number.

780 | CHAPTER 13: GLOSSARY

I n d e x
A absolute pressure 538, 606 transport of diluted species 344
activation overpotential 233, 240, 264 Arrhenius parameters 429
activity dependence 122 atmosphere/gauge (node) 579
additional porous electrode material average linear velocity 644
(node) 129
B base node 314
adsorption 373, 384
battery with binary electrolyte interface
ammeter (node) 307
89
amperometric sensing 261
theory 145
analyte 261
bipolar junction transistor 314
anodes 40
boundary current source (node) 227, 297
anodic Tafel equation 243
boundary electrolyte potential 214, 453
anodic transfer coefficient 234
boundary nodes
Application Libraries window 32
battery interfaces 120
application library examples
Brinkman equations 600
battery with binary electrolyte inter-
Darcy’s law interface 560
face 92
electric currents 292
contact impedance 300
electrochemistry interfaces 198
convection and diffusion 351
electrode, shell 224
Darcy’s law 560
electrostatics 274
electric currents 292
free and porous media flow 589
electrical circuits 69
surface reactions 457
electrolyte-electrode domain interface
transport of concentrated species 398
207, 222
transport of diluted species 345, 449
electrostatics 274
boundary stress (node) 551
infinite electrolyte 184
Brinkman equations 647
laminar flow 536
Brinkman equations interface 597
lead-acid battery interface 85, 97, 105,
theory 647
109, 114, 116
bulk node 315
lithium-ion battery interface 83, 773
Butler-Volmer and Tafel expressions
migration in electric field 351
tertiary current distribution 188
secondary current distribution 181
Butler-Volmer equation 49
storage model 583
electrode kinetics 240
surface reactions 457
secondary current distribution 233
tertiary current distribution,
Butler–Volmer equation
Nernst-Planck 192
electroanalysis 266
transport of concentrated species 397

INDEX| 781
 C capacitor (node) 308 current source (node) 226
CAPE-OPEN compliant packages 675 current sources, theory 324
cathodes 40 current-controlled current source
cathodic charge transfer coefficient 234 (node) 311
cathodic Tafel equation 243 current-controlled voltage source
CFL number (node) 311
settings 535, 600 cyclic voltammetry 261
change cross-section (node) 287
D Darcy velocity 490, 574
change thickness (out-of-plane) (node)
Darcy’s law interface 558
288
theory 641
charge conservation (node) 276
Debye length 44
charge conservation, piezoelectric
deforming electrode surface (node) 770
(node) 288
device models, electrical circuits 329
charge discharge cycling (node) 221
diffusion models 393
charge relaxation theory 322
diode (node) 317
charge transfer reaction 233
diode transistor model 335
charge transfer reactions 207
distributed impedance (node) 298
checklist, for modeling 61
documentation 31
chemical equilibrium 426
domain nodes
chronoamperometry 261
battery interfaces, shared 120
circuit import, SPICE 320
battery with binary electrolyte 93
collector node 314
Brinkman equations 600
common settings 31
Darcy’s law 560
concentration (node)
electric currents 292
battery interfaces 131
electrochemistry interfaces 198
transport of diluted species 355
electrophoretic transport interface
conduction loss (time-harmonic) (node)
449
278
electrostatics 274
contact impedance (node) 299
free and porous media flow 589
convection 490
lead-acid battery 97
convective terms, diluted species 482
transport of concentrated species 398
coulometry 261
transport of diluted species 345
coupling, to the electrical circuits inter-
double layer capacitance (node) 212
face 70
drain node 315
creeping flow (spf) interface 530
Dusty gas model 394
critical point 692
current (node) 452 E edge electrode (node) 185

current density (node) 452 edge nodes

battery interfaces 120

782 | I N D E X
 Darcy’s law interface 560 electrode power (node) 218
electric currents 292 electrode reaction (node)
electrochemistry interfaces 198 battery interfaces 84
electrode, shell 224 electrochemistry 207
electrostatics 274 electrode surface (node) 203
surface reactions 457 electrode symmetry axis current source
electric currents interface 290 (node) 186
theory 326 electrode, shell interface 223
electric displacement field (node) 282 theory 259
electric fields theory 322 electrode-electrolyte boundary interface
electric insulation (node) (node)
electrode, shell 227 current distribution 216
electric potential 134 electrode-electrolyte interface coupling
electric potential (node) 280 (node)
electrode, shell 228 free and porous media flow 571, 595
electric reference potential (node) 221 transport of diluted species 366, 407
electrical circuit interface 305 electrode-electrolyte interfaces 40
theory 328 electrodes 39
electrical circuits electrolysis 39
modeling techniques 69 electrolyte 232
electroanalysis interface 229 electrolyte (node)
theory 261 battery interfaces 121
electroanalysis, definition 261 primary and secondary current distri-
electrochemical cells 40 bution 181
electrochemical impedance spectrosco- tertiary current distribution 193
py (EIS) 261 electrolyte current (node) 214
electrochemical sensing 261 electrolyte current density (node) 215
electrode 232 electrolyte current source (node) 201
electrode (node) electrolyte line current source (node)
electrochemistry 200 186
electrode, shell 225 electrolyte points current source (node)
electrode current (node) 217 187
electrode current density (node) 217 electrolyte potential 235
electrode current source (node) 200 electrolyte potential (node) 214
electrode line current source (node) 186 electrolyte symmetry axis current
electrode points current source (node) source (node) 187
187 electrolyte-electrode domain interface
electrode potential (node) 219 (node) 213

INDEX| 783
 electrolytes 39 flash calculation
electrolytes, salt concentration 134 retrograde solution type 692
electromagnetic heat source (multiphys- solution type 692–693
ics coupling) 772 flash calculations 690
electroneutrality 44 flow continuity (node) 555
electrophoretic transport interface 443 flow rate in SCCMs 546
electrostatics interface 272 fluid flow
theory 322 Brinkman equations theory 647
elevation 570 fluid properties (node) 590
emailing COMSOL 32 flux (node) 387, 454
emitter node 314 battery interfaces 131
EnthalpyF 692 transport of concentrated species 411
EntropyF 692 transport of diluted species 355, 387,
equation of continuity 322 454
equilibrium potential 233 flux discontinuity (node) 357
Equilibrium Reaction Darcy’s law 576
theory for 480 transport of concentrated species 417
equilibrium reaction (node) 362, 418 transport of diluted species 357
equilibrium reaction group (node) 438 fracture flow (node) 581
error message, electrical circuits 69 free and porous media flow interface 587
exporting theory 646
SPICE netlists 74 Freundlich exponent 496
external I vs. U (node) 317 fully developed flow 546
external I-terminal (node) 319
G galvanic cells 39
external short circuit (node) 219
gas constant 528
external surface charge accumulation
gas diffusion 502
(node) 281
gas reacting fluids 421, 433
external thermodynamic packages 675
gate node 315
external U vs. I (node) 318
Gauss’ law and charge relaxation theory
extra dimensions 79, 89
322
F faradaic current 53 Gauss’ law equation 324
Faraday’s constant 234 general stress (boundary stress condi-
Faraday’s law 487 tion) 552
Faraday’s laws of electrolysis 265 Gibbs free energy 431
Fick diffusion laws 263 gravity 557
Fick equations and diffusivities 502 ground (node) 227, 279
Fick’s law approximation diffusion 508 ground node (node) 306
Fick’s law diffusion model 395
H harmonic perturbation (node) 218

784 | I N D E X
 heterogeneous rate constant 266 knowledge base, COMSOL 33
hydraulic head (node) 578 Knudsen diffusion 394
Hygroscopic Swelling 376
L laminar flow interface 531
I importing Langmuir constant 496
SPICE netlists 73, 320 lead-acid battery interface 95
inductor (node) 308 theory 153
inflow (node) 354, 455 leaking wall, wall boundary condition
transport of concentrated species 413 541, 596
initial cell charge distribution (node) 131 line charge (node) 284
initial values (node) line charge (on axis) (node) 285
battery with binary electrolyte 93 line charge (out-of-plane) (node) 285
Brinkman equations 605 line current source (node) 301
corroding electrode surface node 220 line current source (on axis) (node) 302
Darcy’s law 568 line mass source (node)
depositing electrode surface node 220 fluid flow 556
electric currents 296 species transport 360
electrode, shell 226 line source
electrostatics 278 species transport 484
free and porous media flow 594 liquid reacting fluids 421, 433
lead-acid battery 98 lithium-ion battery interface 79
lithium-ion battery 83 theory 134
primary and secondary current distri- local
bution 182 CFL number 535, 600
single-phase, laminar flow 539
M mass action law, laminar flow 527
spf interfaces 539
mass based concentrations (node) 351
surface reactions 459
mass fraction (node) 411
tertiary current distribution 195
mass source (node)
transport of concentrated species 410
Brinkman equations 604
transport of diluted species 351
Darcy’s law 567
inlet (node) 543
mass transport 501
single-phase flow 543
Maxwell’s equations
insulation (node) 202, 453
electrical circuits and 328
intercalating species 122
Maxwell-Stefan diffusion model 394
intercalation diffusivity 125
Maxwell-Stefan diffusivity matrix 505
internet resources 31
mixture-averaged diffusion model 394,
intrinsic volume averages 647
506
irreversible reaction 426
modeling checklist 61
K Kirchhoff’s circuit laws 328 monolayer adsorption 518

INDEX| 785
 MPH-files 32 ohmic drop 262
multicomponent diffusion 504 open boundary (node)
multiphase flash calculations 676 single-phase flow 550
multiphysics couplings spf interfaces 550
electromagnetic heat source (node) transport of concentrated species 417
772 transport of diluted species 361
mutual inductance (node) 315 outflow (node)
electrophoretic transport 455
N n-Channel MOS transistor 314, 332
transport of concentrated species 416
n-Channel MOSFET (node) 314
transport of diluted species 354
negative electrode selection (node) 133
outlet (node) 547
negative porous electrode (node) 99
single-phase flow 547
Nernst equation 266
spf interfaces 547
Nernst-Einstein relation 350, 368, 372,
overpotential 48, 233
486
Nernst-Planck equations 43, 230 P pair contact impedance (node) 299
Nernst-Planck-Poisson equations 44 pair nodes
Nernst-Planck-Poisson Equations inter- battery interfaces 120
face 441 Brinkman equations 600
netlists, SPICE 73, 320 Darcy’s law interface 560
no flow (node) 576 electric currents 292
no flux (node) 353 electrochemistry interfaces 198
battery interfaces 131 electrode, shell 224
transport of concentrated species 414 electrophoretic transport interface
no slip, wall boundary condition 540, 596 449
no viscous stress (open boundary) 551 electrostatics 274
nodes, common settings 31 free and porous media flow 589
nonconservative formulations 482 surface reactions 457
nondeforming boundary (node) 771 transport of concentrated species 398
non-faradaic reactions 129 transport of diluted species 345
non-faradaic reactions (node) 220 partially saturated porous media (node)
normal current density (node) 227 370
normal stress, normal flow (boundary particle intercalation 122
stress condition) 552 p-Channel MOS transistor 314
NPN bipolar junction transistor 329 p-Channel MOSFET (node) 314
NPN BJT (node) 314 periodic condition (node) 184
transport of diluted species 358
O Ohm’s law 178, 232, 487
periodic flow condition (node) 553
Ohm’s law and charge relaxation theory
permeability models 566, 585
322

786 | I N D E X
persistence porous media and subsurface flow
of thermodynamic packages 679 Brinkman equations interface 597
pervious layer (node) 579 Darcy’s law interface 558
physics interfaces, common settings 31 free and porous media flow interface
PNP BJT (node) 314 587
point charge (node) 286 theory, Brinkman equations 647
point charge (on axis) (node) 287 theory, free and porous media flow
point current source (node) 302 646
point current source (on axis) (node) porous media transport properties
303 (node) 366, 370, 404
point mass source (node) Porous Medium (node)
fluid flow 556 Brinkman equations 591, 601
species transport 360 positive electrode selection (node) 133
point nodes positive porous electrode (node) 99
battery interfaces 120 potential (node) 453
Brinkman equations 600 potentiometry 261
Darcy’s law interface 560 potentiostat 269
electric currents 292 predefined couplings, electrical circuits
electrochemistry interfaces 198 70
electrode, shell 224 pressure (node) 572, 575, 577
electrostatics 274 pressure head (node) 578
free and porous media flow 589 pressure point constraint (node) 555
surface reactions 457 primary current distribution 41
transport of diluted species 345 primary current distribution interface
point source 178
species transport 483 theory 230
porous conductive binder (node) 129 pseudo time step 525
porous electrode (node) 182, 194 pseudo time stepping
battery interfaces 122 settings 535, 600
porous electrode coupling (node) 364
Q quiescent binary electrolytes
free and porous media flow 571, 594
battery with binary electrolyte inter-
porous electrode reaction (node) 127,
face 145
201
lithium-ion battery interface 134
porous electrodes 137, 181, 233
R reacting fluids, gases and liquids 421, 433
porous matrix adsorption/desorption
Reacting Volume 352, 389
reaction (node) 93
reaction (node) 425
porous matrix double layer capacitance
reaction coefficients (node) 365
(node) 202
reaction source (node) 128

INDEX| 787
 reaction thermodynamics (node) 439 species activity (node) 439
reactions (node) species group (node) 439
surface reactions 459 species source (node) 453
tertiary current distribution 195 species thermodynamics (node) 440
transport of concentrated species 409 SPICE
transport of diluted species 352 exporting 74
reference electrode (node) 220 SPICE netlists 73, 320
reservoir (node) 98 standard cubic centimeters per minute
resistive film 149, 239 546
resistor (node) 307 standard flow rate 546
retardation factor 496 standard settings 31
reversible reaction 426 stoichiometric coefficients 147, 431
reversible reaction group (node) 436 Stokes equations 530
Reynolds number 466 Stokes flow 530
stratified porous media 494
S SCCM, flow rate in 546
subcircuit definition (node) 313
secondary current distribution 41
subcircuit instance (node) 313
secondary current distribution interface
superficial volume average, porous me-
178
dia 647
theory 230
superficial volume averages, porous me-
sector symmetry (node) 300
dia 490
SEI 124, 131
supporting electrolyte 261
SEMI standard E12-0303 545
Supporting Electrolytes 486
semiconductor device models 329
surface charge density (node) 280
separator (node)
surface concentration (node) 460
battery with binary electrolyte inter-
surface equilibrium reaction (node) 364,
face 122
419
current distribution 195
surface properties (node) 458
lead battery interface 100
surface reactions interface 456
single-phase flow interface
theory 517
laminar flow 531
switch (node) 312
sliding wall 542
symmetry (node) 550
slip, wall boundary condition 541, 596
Darcy’s law 575
solid electrolyte interface 124, 131
electrochemistry 202
solid-electrolyte interface, SEI 149
spf interfaces 550
Soret effect 509
transport of concentrated species 416
source node 315
transport of diluted species 357
space charge density (node) 279
symmetry plane (node) 281
species (node) 431

788 | I N D E X
T Tafel equation 243 fracture 379
Tafel law 49 out-of-plane 571
technical support, COMSOL 32 thin diffusion barrier (node) 361
tertiary current distribution 41 Thin Impermeable Barrier 362
tertiary current distribution interface thin low permittivity gap (node) 284
theory 230 tortuosity factors 492
tertiary current distribution, traction boundary conditions 551
Nernst-Planck interface 188 transference number 121
theory transformer (node) 315
battery with binary electrolyte 145 transport mechanisms 400, 406
Brinkman equations 647 transport number 121, 145
Darcy’s law 641 transport of concentrated species in po-
electric currents interface 326 rous media interface 397
electric fields 322 transport of concentrated species inter-
electrical circuit interface 328 face 391
electroanalysis interface 261 theory 501
electrode, shell interface 259 transport of diluted species in porous
electrostatics interface 322 media interface 344
free and porous media flow 646 theory 479
lead-acid battery 153 transport of diluted species interface
lithium-ion battery 134 340, 381
primary current distribution interface theory 478
230 turbulent Prandtl number 466
secondary current distribution inter-
V voltage source (node) 308
face 230
voltage-controlled current source
surface reactions 517
(node) 311
tertiary current distribution interface
voltage-controlled voltage source (node)
230
310
transport of concentrated species in-
voltammetry, cyclic 261
terface 501
voltmeter (node) 307
transport of diluted species in porous
volume averages 647
media interface 479
volume force (node) 539, 605
transport of diluted species interface
free and porous media flow 593
478
spf interfaces 539
thermal diffusion 509
W wall (node)
thermodynamics package 675
adding 676 free and porous media flow 595

thickness single-phase flow 540

websites, COMSOL 32

INDEX| 789
 Z zero charge (node) 279

790 | I N D E X