Chemical Reaction

Engineering Module
User’s Guide
Chemical Reaction Engineering Module User’s Guide
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Part number: CM021601

C o n t e n t s

Chapter 1: User’s Guide Introduction

About the Chemical Reaction Engineering Module 14

The Scope of the Chemical Reaction Engineering Module . . . . . . . 14
The Chemical Reaction Engineering Module Physics Interface Guide . . . 15
The Material Database . . . . . . . . . . . . . . . . . . . . . 19
Common Physics Interface and Feature Settings and Nodes . . . . . . 19
Where Do I Access the Documentation and Application Libraries? . . . . 19

Overview of the User’s Guide 23

Chapter 2: The Chemistry and Reaction Engineering

Interfaces

Overview of the Reaction Engineering and Chemistry

interfaces 26
Using the Reaction Node. . . . . . . . . . . . . . . . . . . . 27
Using the Species Node . . . . . . . . . . . . . . . . . . . . 30
Using the Equation View Node - Reactions and Species . . . . . . . . 32

Theory for the Reaction Engineering and Chemistry Interfaces

34
Reaction Kinetics and Rate Expressions . . . . . . . . . . . . . . 34
The Equilibrium Constant . . . . . . . . . . . . . . . . . . . 35
Handling of Equilibrium Reactions . . . . . . . . . . . . . . . . 39
Reactor Types in the Reaction Engineering Interface . . . . . . . . . 42
Transport Properties . . . . . . . . . . . . . . . . . . . . . 49
CHEMKIN Data and NASA Polynomials . . . . . . . . . . . . . . 53
Working with Predefined Expressions . . . . . . . . . . . . . . . 54
References for the Reaction Engineering Interface . . . . . . . . . . 56

CONTENTS |3
 The Reaction Engineering Interface 58
Features Nodes Available for the Reaction Engineering Interface . . . . . 66
Initial Values . . . . . . . . . . . . . . . . . . . . . . . . 66
Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . 67
Species . . . . . . . . . . . . . . . . . . . . . . . . . . 71
Reversible Reaction Group . . . . . . . . . . . . . . . . . . . 75
Equilibrium Reaction Group. . . . . . . . . . . . . . . . . . . 77
Species Group . . . . . . . . . . . . . . . . . . . . . . . . 78
Additional Source . . . . . . . . . . . . . . . . . . . . . . 79
Reaction Thermodynamics . . . . . . . . . . . . . . . . . . . 80
Species Activity . . . . . . . . . . . . . . . . . . . . . . . 80
Species Thermodynamics. . . . . . . . . . . . . . . . . . . . 80
Feed Inlet. . . . . . . . . . . . . . . . . . . . . . . . . . 81
Generate Space-Dependent Model . . . . . . . . . . . . . . . . 82
Parameter Estimation . . . . . . . . . . . . . . . . . . . . . 90
Experiment . . . . . . . . . . . . . . . . . . . . . . . . . 91

The Chemistry Interface 94

Feature Nodes Available for the Chemistry Interface . . . . . . . . . 97
Reaction . . . . . . . . . . . . . . . . . . . . . . . . . . 98
Species . . . . . . . . . . . . . . . . . . . . . . . . . 102
Reversible Reaction Group . . . . . . . . . . . . . . . . . . 105
Equilibrium Reaction Group. . . . . . . . . . . . . . . . . . 106
Species Group . . . . . . . . . . . . . . . . . . . . . . . 108
Reaction Thermodynamics . . . . . . . . . . . . . . . . . . 108
Species Activity . . . . . . . . . . . . . . . . . . . . . . 109
Species Thermodynamics. . . . . . . . . . . . . . . . . . . 109

Study Steps for the Reaction Engineering Interface 110

Reactor Types and Solver Study Steps . . . . . . . . . . . . . . 110
Solver Study Steps for Parameter Estimation . . . . . . . . . . . 110

Chapter 3: Chemical Species Transport Interfaces

Overview of Chemical Species Transport Interfaces 115

Available Physics Interfaces . . . . . . . . . . . . . . . . . . 115

4 | CONTENTS
Coupling to Other Physics Interfaces . . . . . . . . . . . . . . 117
Adding a Chemical Species Transport Interface and Specifying the
Number of Species . . . . . . . . . . . . . . . . . . . . 117

Theory for the Transport of Diluted Species Interface 120

Mass Balance Equation . . . . . . . . . . . . . . . . . . . . 121
Equilibrium Reaction Theory . . . . . . . . . . . . . . . . . 122
Convective Term Formulation. . . . . . . . . . . . . . . . . 124
Solving a Diffusion Equation Only . . . . . . . . . . . . . . . 124
Mass Sources for Species Transport . . . . . . . . . . . . . . 125
Adding Transport Through Migration . . . . . . . . . . . . . . 127
Supporting Electrolytes . . . . . . . . . . . . . . . . . . . 128
Crosswind Diffusion . . . . . . . . . . . . . . . . . . . . 129
Danckwerts Inflow Boundary Condition . . . . . . . . . . . . . 130
Mass Balance Equation for Transport of Diluted Species in Porous
Media . . . . . . . . . . . . . . . . . . . . . . . . . 131
Convection in Porous Media . . . . . . . . . . . . . . . . . 132
Diffusion in Porous Media . . . . . . . . . . . . . . . . . . 134
Dispersion . . . . . . . . . . . . . . . . . . . . . . . . 135
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . 137
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 138
Mass Transport in Fractures . . . . . . . . . . . . . . . . . 139
Theory for the Reactive Pellet Bed . . . . . . . . . . . . . . . 140
References . . . . . . . . . . . . . . . . . . . . . . . . 148

Theory for the Transport of Concentrated Species Interface 150

Multicomponent Mass Transport . . . . . . . . . . . . . . . . 150
Multicomponent Gas Diffusion: Maxwell-Stefan Description . . . . . 151
Multicomponent Diffusivities . . . . . . . . . . . . . . . . . 153
Multicomponent Diffusion: Mixture-Averaged Approximation . . . . . 155
Multispecies Diffusion: Fick’s Law Approximation . . . . . . . . . 157
Multicomponent Thermal Diffusion . . . . . . . . . . . . . . . 158
Regularization of Reaction Rate Expression . . . . . . . . . . . . 158
References for the Transport of Concentrated Species Interface . . . . 159

CONTENTS |5
 Theory for the Electrophoretic Transport Interface 160

Theory for the Surface Reactions Interface 166

Governing Equations for the Surface Concentrations . . . . . . . . 166
Governing Equations for the Bulk Concentrations . . . . . . . . . 167
ODE Formulations for Surface Concentrations . . . . . . . . . . 169
Surface Reaction Equations on Deforming Geometries . . . . . . . 170
Reference for the Surface Reactions Interface . . . . . . . . . . . 171

Theory for the Nernst-Planck Equations Interface 172

Governing Equations for the Nernst-Planck Formulation . . . . . . . 172
Convective Term Formulation. . . . . . . . . . . . . . . . . 174

Theory for the Reacting Laminar Flow Interface 175

Pseudo Time Stepping for Mass Transport . . . . . . . . . . . . 175
The Stefan Velocity . . . . . . . . . . . . . . . . . . . . . 175
The Chemical Reaction Rate . . . . . . . . . . . . . . . . . 177

The Transport of Diluted Species Interface 179

The Transport of Diluted Species in Porous Media Interface . . . . . 183
Domain, Boundary, and Pair Nodes for the Transport of Diluted
Species Interface. . . . . . . . . . . . . . . . . . . . . 184
Transport Properties . . . . . . . . . . . . . . . . . . . . 186
Turbulent Mixing . . . . . . . . . . . . . . . . . . . . . . 188
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 189
Mass-Based Concentrations . . . . . . . . . . . . . . . . . . 189
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 189
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 191
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 191
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 192
Concentration . . . . . . . . . . . . . . . . . . . . . . . 192
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 192
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 193
Flux Discontinuity . . . . . . . . . . . . . . . . . . . . . 193
Partition Condition . . . . . . . . . . . . . . . . . . . . . 194
Periodic Condition . . . . . . . . . . . . . . . . . . . . . 195
Line Mass Source . . . . . . . . . . . . . . . . . . . . . . 195
Point Mass Source . . . . . . . . . . . . . . . . . . . . . 196

6 | CONTENTS
Open Boundary . . . . . . . . . . . . . . . . . . . . . . 197
Thin Diffusion Barrier . . . . . . . . . . . . . . . . . . . . 197
Thin Impermeable Barrier . . . . . . . . . . . . . . . . . . 197
Equilibrium Reaction . . . . . . . . . . . . . . . . . . . . 198
Surface Reactions . . . . . . . . . . . . . . . . . . . . . 199
Surface Equilibrium Reaction . . . . . . . . . . . . . . . . . 199
Fast Irreversible Surface Reaction . . . . . . . . . . . . . . . 200
Porous Electrode Coupling . . . . . . . . . . . . . . . . . . 200
Reaction Coefficients . . . . . . . . . . . . . . . . . . . . 201
Electrode Surface Coupling . . . . . . . . . . . . . . . . . . 201
Porous Media Transport Properties. . . . . . . . . . . . . . . 202
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . 204
Partially Saturated Porous Media . . . . . . . . . . . . . . . . 205
Volatilization . . . . . . . . . . . . . . . . . . . . . . . 207
Reactive Pellet Bed . . . . . . . . . . . . . . . . . . . . . 208
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 211
Species Source. . . . . . . . . . . . . . . . . . . . . . . 212
Hygroscopic Swelling . . . . . . . . . . . . . . . . . . . . 213
Fracture . . . . . . . . . . . . . . . . . . . . . . . . . 213

The Transport of Diluted Species in Fractures Interface 215

Boundary, Edge, Point, and Pair Nodes for the Transport of Diluted
Species in Fractures Interface . . . . . . . . . . . . . . . . 217
Adsorption . . . . . . . . . . . . . . . . . . . . . . . . 218
Concentration . . . . . . . . . . . . . . . . . . . . . . . 219
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
Fracture . . . . . . . . . . . . . . . . . . . . . . . . . 219
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 220
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 221
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 221
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 221
Species Source. . . . . . . . . . . . . . . . . . . . . . . 222

The Transport of Concentrated Species Interface 223

Domain, Boundary, and Pair Nodes for the Transport of
Concentrated Species Interface . . . . . . . . . . . . . . . 229
Transport Properties . . . . . . . . . . . . . . . . . . . . 230
Porous Media Transport Properties. . . . . . . . . . . . . . . 234

CONTENTS |7
 Electrode Surface Coupling . . . . . . . . . . . . . . . . . . 237
Turbulent Mixing . . . . . . . . . . . . . . . . . . . . . . 238
Reaction . . . . . . . . . . . . . . . . . . . . . . . . . 239
Reaction Sources . . . . . . . . . . . . . . . . . . . . . . 240
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 241
Mass Fraction . . . . . . . . . . . . . . . . . . . . . . . 242
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 243
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 244
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 244
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 245
Flux Discontinuity . . . . . . . . . . . . . . . . . . . . . 245
Open Boundary . . . . . . . . . . . . . . . . . . . . . . 246
Equilibrium Reaction . . . . . . . . . . . . . . . . . . . . 246
Surface Equilibrium Reaction . . . . . . . . . . . . . . . . . 247

The Nernst-Planck Equations Interface 249

Domain and Boundary Nodes for the Nernst-Planck Equations
Interface. . . . . . . . . . . . . . . . . . . . . . . . 252
Convection, Diffusion, and Migration . . . . . . . . . . . . . . 253
Electric Insulation . . . . . . . . . . . . . . . . . . . . . 255
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 255
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 255
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 255
Concentration . . . . . . . . . . . . . . . . . . . . . . . 256
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 256
Symmetry . . . . . . . . . . . . . . . . . . . . . . . . 257
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 257
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 258
Flux Discontinuity . . . . . . . . . . . . . . . . . . . . . 258
Current Density . . . . . . . . . . . . . . . . . . . . . . 258
Current Discontinuity . . . . . . . . . . . . . . . . . . . . 259
Open Boundary . . . . . . . . . . . . . . . . . . . . . . 259
Reference for the Nernst Planck Equations Interface . . . . . . . . 260

8 | CONTENTS
The Nernst-Planck-Poisson Equations Interface 261

The Electrophoretic Transport Interface 262

Common Settings for the Species nodes in the Electrophoretic
Transport Interface . . . . . . . . . . . . . . . . . . . 266
Diffusion and Migration Settings . . . . . . . . . . . . . . . . 267
Domain, Boundary, and Pair Nodes for the Electrophoretic Transport
Interface. . . . . . . . . . . . . . . . . . . . . . . . 268
Solvent . . . . . . . . . . . . . . . . . . . . . . . . . 269
Porous Matrix Properties . . . . . . . . . . . . . . . . . . 269
Fully Dissociated Species . . . . . . . . . . . . . . . . . . . 270
Uncharged Species . . . . . . . . . . . . . . . . . . . . . 270
Weak Acid . . . . . . . . . . . . . . . . . . . . . . . . 270
Weak Base . . . . . . . . . . . . . . . . . . . . . . . . 270
Ampholyte . . . . . . . . . . . . . . . . . . . . . . . . 271
Protein . . . . . . . . . . . . . . . . . . . . . . . . . 271
Current Source . . . . . . . . . . . . . . . . . . . . . . 271
Initial Potential. . . . . . . . . . . . . . . . . . . . . . . 271
Current . . . . . . . . . . . . . . . . . . . . . . . . . 272
Current Density . . . . . . . . . . . . . . . . . . . . . . 272
Insulation . . . . . . . . . . . . . . . . . . . . . . . . . 272
Potential . . . . . . . . . . . . . . . . . . . . . . . . . 272
Species Source. . . . . . . . . . . . . . . . . . . . . . . 273
Initial Concentration . . . . . . . . . . . . . . . . . . . . 273
Concentration . . . . . . . . . . . . . . . . . . . . . . . 273
No Flux . . . . . . . . . . . . . . . . . . . . . . . . . 273
Flux . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
Inflow . . . . . . . . . . . . . . . . . . . . . . . . . . 274
Outflow . . . . . . . . . . . . . . . . . . . . . . . . . 275

The Surface Reactions Interface 276

Boundary, Edge, Point, and Pair Nodes for the Surface Reactions
Interface. . . . . . . . . . . . . . . . . . . . . . . . 277
Surface Properties . . . . . . . . . . . . . . . . . . . . . 278
Initial Values . . . . . . . . . . . . . . . . . . . . . . . 279
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . 279
Surface Concentration . . . . . . . . . . . . . . . . . . . . 280

CONTENTS |9
 The Reacting Flow Multiphysics Interface 281
The Reacting Laminar Flow Interface . . . . . . . . . . . . . . 281
The Reacting Flow Coupling Feature . . . . . . . . . . . . . . 282
Physics Interface Features . . . . . . . . . . . . . . . . . . 284

The Reacting Flow in Porous Media Multiphysics Interface 286

The Reacting Flow in Porous Media, Transport of Diluted Species
Interface. . . . . . . . . . . . . . . . . . . . . . . . 286
The Reacting Flow in Porous Media, Transport of Concentrated
Species Interface. . . . . . . . . . . . . . . . . . . . . 287
The Reacting Flow, Diluted Species Coupling Feature . . . . . . . . 287
The Reacting Flow Coupling Feature . . . . . . . . . . . . . . 288
Physics Interface Features . . . . . . . . . . . . . . . . . . 288

Chapter 4: Fluid Flow Interfaces

Modeling Fluid Flow 290

Available Physics Interfaces . . . . . . . . . . . . . . . . . . 290
Coupling to Other Physics Interfaces . . . . . . . . . . . . . . 291

Chapter 5: Heat Transfer Interfaces

Modeling Heat Transfer 294

Available Physics Interfaces . . . . . . . . . . . . . . . . . . 294
Coupling Heat Transfer with Other Physics Interfaces. . . . . . . . 294

Chapter 6: Thermodynamics

Using Thermodynamic Properties 296

Workflow for Thermodynamics Property Calculations . . . . . . . 296
Thermodynamics . . . . . . . . . . . . . . . . . . . . . . 297
Thermodynamic System . . . . . . . . . . . . . . . . . . . 299
External Thermodynamic Packages . . . . . . . . . . . . . . . 308

10 | C O N T E N T S
 External Thermodynamic System . . . . . . . . . . . . . . . . 309
Exporting and Importing Thermodynamic Systems . . . . . . . . . 313
Species Property . . . . . . . . . . . . . . . . . . . . . . 313
Mixture Property. . . . . . . . . . . . . . . . . . . . . . 319
Equilibrium Calculation . . . . . . . . . . . . . . . . . . . 321
Coupling with the Reaction Engineering and the Chemistry Interfaces . . 326
Evaluating a Property Function in a Physics Interface . . . . . . . . 330
User Defined Species . . . . . . . . . . . . . . . . . . . . 331
References . . . . . . . . . . . . . . . . . . . . . . . . 339

Thermodynamic Models and Theory 340

Introduction . . . . . . . . . . . . . . . . . . . . . . . 340
Thermodynamic Models . . . . . . . . . . . . . . . . . . . 340
Selecting the Right Thermodynamic Model . . . . . . . . . . . . 355
Thermodynamic Properties Definitions . . . . . . . . . . . . . 357
Standard Enthalpy of Formation and Absolute Entropy terms . . . . . 360
Reference State . . . . . . . . . . . . . . . . . . . . . . 362
Transport Properties . . . . . . . . . . . . . . . . . . . . 362
Surface Tension . . . . . . . . . . . . . . . . . . . . . . 375
References . . . . . . . . . . . . . . . . . . . . . . . . 375

Chapter 7: Glossary

Glossary of Terms 382

CONTENTS | 11
12 | C O N T E N T S
 1

User’s Guide Introduction

This guide describes the Chemical Reaction Engineering Module, an optional

package that extends the COMSOL Multiphysics® modeling environment with
customized physics interfaces and functionality for the analysis of mass transport,
chemical reactions, thermodynamic properties, and other features that are
important for chemical engineering simulation.

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 Chemical Reaction Engineering Module

• Overview of the User’s Guide

13
 About the Chemical Reaction
Engineering Module
In this section:

• The Scope of the Chemical Reaction Engineering Module

• The Chemical Reaction Engineering Module Physics Interface Guide
• Common Physics Interface and Feature Settings and Nodes
• The Material Database
• Where Do I Access the Documentation and Application Libraries?

The Scope of the Chemical Reaction Engineering Module

The Chemical Reaction Engineering Module is tailor-made for the modeling of
chemical systems primarily affected by chemical composition, reaction kinetics, fluid
flow, and temperature as functions of space, time, and each other. It has a number of
physics interfaces to model chemical reaction kinetics, mass transport in dilute,
concentrated, and electric potential-affected solutions, laminar and porous media
flows, and energy transport.

Included in these physics interfaces are the kinetic expressions for the reacting systems
and models for the definition of mass transport. A variety of ready-made expressions
are also accessible in order to calculate a system’s thermodynamic and transport
properties.

Like all COMSOL modules, the physics interfaces described in this guide include all
the steps available for the modeling process, which are described in detail in the
COMSOL Multiphysics Reference Manual (see Where Do I Access the
Documentation and Application Libraries?), for example:

• Definitions of parameters and model variables.

• Creating, importing, and manipulating a geometry.
• Specifying the chemical and transport material properties.
• Defining the reaction formulas and physics in the system and on boundaries, and
coupling them to other features.

14 | CHAPTER 1: USER’S GUIDE INTRODUCTION

• Meshing a modeling domain with appropriate consideration given to the reaction
system’s behavior.
• Solving the equations that describe a system for stationary or dynamic behavior, or
as a parametric or optimization study.
• Analyzing results to present for further use.

Once a model is defined, you can go back and make changes to all the branches listed
above, while maintaining consistency in the other definitions throughout. You can
restart the solver, for example, using the existing solution as an initial guess or even
alter the geometry, while the equations and boundary conditions are kept consistent
through the associative geometry feature. It is also useful to review the Introduction
to the Chemical Reaction Engineering Module included with the module’s
documentation.

While a major focus of this module is on chemical reactors and reacting systems, it is
also extensively used for systems where mass transport is the major component. This
includes unit operations equipment, separation and mixing processes, corrosion,
chromatography, and electrophoresis. The module is also widely used for educational
purposes including courses about chemical engineering, chemical reaction
engineering, electrochemical engineering, biotechnology, and transport phenomena.

In addition to its application in traditional chemical industries, it is a popular tool for

investigating clean technology processes (for example, catalytic monoliths and reactive
filters), applications such as microlaboratories in biotechnology, and in the
development of sensors and equipment in analytical chemistry.

The notations and structure in this module were inspired by the book
Transport Phenomena by Bird, Stewart, and Lightfoot. The work by H.
Scott Fogler, Elements of Chemical Reaction Engineering, was also used
as an inspiration.

The Chemical Reaction Engineering Module Physics Interface Guide

The appropriate physics interface for modeling a system is first chosen from the Model
Wizard. The branches are visible (AC/DC, Acoustics, Structural Mechanics, and
Mathematics) as well as the core physics interfaces (Electrostatics, for example)
included with COMSOL Multiphysics. The Heat Transfer in Fluids, Single-Phase
Flow, Laminar Flow, and Transport of Diluted Species interfaces are also included in

ABOUT THE CHEMICAL REACTION ENGINEERING MODULE | 15

 the base package but have increased functionality with this module. See the COMSOL
Multiphysics Reference Manual for details pertaining to the base package.

• Modeling Fluid Flow

• Modeling Heat Transfer
• Creating a New Model in the COMSOL Multiphysics Reference
Manual

When one or several physics interfaces are chosen from the Model Wizard (or if you
open the Add Study window), you select an analysis type (stationary, dynamic, or
parametric) and then the modeling interface(s) are available as a node(s) in the Model
Builder along with all the other nodes required for modeling (Definitions, Geometry,
and so forth).

By adding another physics interface, you can account for a phenomenon not previously
described in a model. To do this, right-click a Component node in the Model Builder to
open the Add Physics window. You can do this at any stage during the modeling
process. This action still retains the existing geometry, equations, boundary
conditions, and current solution, which you can build upon for further development
of the model.

The table below lists all the physics interfaces specifically available or enhanced with
this module (in addition to the basic COMSOL Multiphysics license). These physics
interfaces form the backbone of the module and are based on the equations for
chemical reaction kinetics, chemical species transport, as well as for fluid flow and heat
transfer in porous media fundamentals.

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.

16 | CHAPTER 1: USER’S GUIDE INTRODUCTION

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
Species1
Transport of Diluted tds all dimensions stationary; time dependent
Species in Porous Media
Transport of Diluted dsf 3D, 2D, 2D stationary; time dependent
Species in Fractures axisymmetric
Electrophoretic Transport el all dimensions stationary; stationary with
initialization; time
dependent; time dependent
with initialization
Chemistry chem all dimensions stationary; time dependent

Transport of tcs all dimensions stationary; time dependent

Concentrated Species
Nernst-Planck Equations npe all dimensions stationary; time dependent

Nernst-Planck-Poisson tds+es all dimensions stationary; time dependent;

Equations stationary source sweep;
small-signal analysis,
frequency domain
Reaction Engineering re 0D time dependent; stationary
plug flow
Reacting Flow

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

axisymmetric
Laminar Flow, Diluted — 3D, 2D, 2D stationary; time dependent
Species1 axisymmetric

ABOUT THE CHEMICAL REACTION ENGINEERING MODULE | 17

 PHYSICS INTERFACE ICON TAG SPACE AVAILABLE STUDY TYPE
DIMENSION

Reacting Flow in Porous Media

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

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

Single-Phase Flow

Creeping Flow spf 3D, 2D, 2D stationary; time dependent

axisymmetric
Laminar Flow1 spf 3D, 2D, 2D stationary; time dependent
axisymmetric
Porous Media and Subsurface Flow

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

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

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

Flow axisymmetric
Heat Transfer

Heat Transfer in Fluids1 ht all dimensions stationary; time dependent

Heat Transfer in Solids and ht all dimensions stationary; time dependent

Fluids1
Heat Transfer in Porous ht all dimensions stationary; time dependent
Media
1
This physics interface is included with the core COMSOL package but has added
functionality for this module.

18 | CHAPTER 1: USER’S GUIDE INTRODUCTION

The Material Database
The Chemical Reaction Engineering Module includes an additional Liquids and Gases
material database with temperature-dependent fluid dynamic and thermal properties.

• Liquids and Gases Materials Database

• Materials

Common Physics Interface and Feature Settings and Nodes

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

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

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

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

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

Where Do I Access the Documentation and Application Libraries?

A number of internet resources have more information about COMSOL, including
licensing and technical information. The electronic documentation, topic-based (or
context-based) help, and the application libraries are all accessed through the
COMSOL Desktop.

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

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

ABOUT THE CHEMICAL REACTION ENGINEERING MODULE | 19

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

Opening Topic-Based Help

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

To open the Help window:

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

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

To open the Help window:

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

Opening the Documentation Window

To open the Documentation window:

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

20 | CHAPTER 1: USER’S GUIDE INTRODUCTION

 To open the Documentation window:

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

THE APPLICATION LIBRARIES WINDOW

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

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

The Application Libraries Window in the COMSOL Multiphysics

Reference Manual.

Opening the Application Libraries Window

To open the Application Libraries window ( ):

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

Libraries.
• From the File menu select Application Libraries.

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

menu, select ( ) Update COMSOL Application Library.

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

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

ABOUT THE CHEMICAL REACTION ENGINEERING MODULE | 21

 CONTACTING COMSOL BY EMAIL
For general product information, contact COMSOL at info@comsol.com.

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
support@comsol.com. An automatic notification and a case number are sent to you by
email. You can also access technical support, software updates, license information, and
other resources by registering for a COMSOL Access account.

COMSOL ONLINE RESOURCES

COMSOL website www.comsol.com

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

22 | CHAPTER 1: USER’S GUIDE INTRODUCTION

Overview of the User’s Guide
The Chemical Reaction Engineering Module User’s Guide is a consummate guide to
using COMSOL Multiphysics and the add-on module Chemical Reaction Engineering
Module. The information in this guide is specific for this module. Instructions how to
use COMSOL in general are included with the COMSOL Multiphysics Reference
Manual. The Introduction to the Chemical Reaction Engineering Module contains
a quick-start guide to help you get started using this module.

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.

THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

The Reaction Engineering Interface, which is found under the Chemical Species
Transport branch, has all of the tools required to simulate chemical reaction kinetics,
is described in detail for the Theory for the Reaction Engineering and Chemistry
Interfaces.

THE CHEMICAL SPECIES TRANSPORT INTERFACES

The transport and conversion of chemical compounds is denoted as chemical species
transport. Chemical Species Transport Interfaces chapter describes the Transport of
Diluted Species, Transport of Diluted Species in Porous Media, and Transport of
Concentrated Species interfaces, which are used for the simulation of chemical
reactions, and mass chemical compounds transport through diffusion, convection and
electromigration. It also includes the Surface Reactions interface, which models
reactions involving surface adsorbed species and species in the bulk of a reacting
surface. The Nernst-Planck, The Electrophoretic Transport, Reacting Flow, Laminar
Flow, and Transport of Diluted Species in Porous Media interfaces are also described
in this chapter.

The Reacting Flow in Porous Media Multiphysics Interface section, the Reacting Flow
in Porous Media (rfds) and Reacting Flow in Porous Media (rfcs) interfaces are
described. The theory for these physics interfaces is included.

OVERVIEW OF THE USER’S GUIDE | 23

 Overview of Chemical Species Transport Interfaces helps you select the best physics
interface to use. The rest of the chapter describes the physics interfaces in detail as well
as the underlying theory.

THE FLUID FLOW INTERFACES

Fluid Flow Interfaces chapter describes the physics interfaces under the Porous Media
and Subsurface Flow branch, which are the Darcy’s Law, Brinkman Equations, and
Free and Porous Media Flow interfaces. To help you select the physics interface to use,
see Modeling Fluid Flow.

THE HEAT TRANSFER INTERFACES

The chapter describes The Heat Transfer in Porous Media Interface and includes a
section to help choose the right physics interface (Modeling Heat Transfer).

THERMODYNAMICS INPUT
The chapter Thermodynamics describes different ways of how inputting external
thermodynamics information to a model.

24 | CHAPTER 1: USER’S GUIDE INTRODUCTION

 2

The Chemistry and Reaction Engineering

Interfaces
This chapter describes the Chemistry (chem) and Reaction Engineering (re)
interfaces, available in the Chemical Species Transport branch ( ).

In this chapter:

• Overview of the Reaction Engineering and Chemistry interfaces

• Theory for the Reaction Engineering and Chemistry Interfaces
• The Reaction Engineering Interface
• The Chemistry Interface
• Study Steps for the Reaction Engineering Interface

See also Chemical Species Transport Interfaces for the additional physics interfaces
in the Chemical Species Transport branch ( ).

25
 Overview of the Reaction Engineering
and Chemistry interfaces
The Reaction Engineering and Chemistry interfaces share many common features and
functionality for defining species and reactions. The main difference is that the Reaction
Engineering interface always is defined within the context of a (zero dimensional)
reactor model, solving for a number of species dependent variables and an optional
heat balance, whereas the Chemistry interfaces solely defines a number of variable
expressions, based on species and reactions, that can be used when coupling the
Chemistry interface to, for instance, a space-dependent mass transport model.

THE REACTION ENGINEERING INTERFACE

The Reaction Engineering Interface ( ) includes all of the tools required to simulate
chemical reaction kinetics in well-defined environments. This includes the automatic
set up and simulation of reversible, equilibrium, and irreversible reactions in volumes
or on surfaces. A library of predefined reactors is also available, including batch,
continuous stirred-tank, semibatch, and plug flow reactors (see Reactor Types in the
Reaction Engineering Interface). In addition, the Parameter Estimation feature makes
it possible to evaluate kinetic and model parameters from experimental data.

Use the Generate Space-Dependent Model node to create a

space-dependent model based on your model created in the Reaction
Engineering interface. This automatically sets up the mass balances and
source terms for systems where reactions occur, with a copy of all and your
original species and reaction definitions recreated in separate a Chemistry
node.

The Reaction Engineering interface can also be used for defining and simulating
thermodynamic data.

Interfaces to internal or external thermodynamic packages (such as CAPE-OPEN

compliant packages), and an import feature for CHEMKIN® files mean that the
thermodynamic properties within reaction kinetics, as well as mass and heat transfer
applications, can be described by empirical relations and algebraic expressions. Also see
the Theory for the Reaction Engineering and Chemistry Interfaces.

26 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

THE CHEMISTRY INTERFACE
The Chemistry Interface ( ) is a tool for generating a set of variables to be used for
modeling chemical species and reactions systems. The variables are generated from
species and reaction properties and can be divided in two categories:

• Rate expressions and heat sources for use in mass and heat balances
• Material property variables (mixture density, diffusivities, viscosity, etc.) for use in
space-dependent transport equations.

The Chemistry interface is also created when the Generate Space-Dependent Model
feature is used in The Reaction Engineering Interface, collecting all mixture variables
and properties for use in a space-dependent model.

Using the Reaction Node

In each Reaction node, specify the reaction Formula and Reaction type of a single
chemical reaction.

For each reaction formula entered, 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

OVERVIEW OF THE REACTION ENGINEERING AND CHEMISTRY INTERFACES | 27

 It is also possible to adjust the reaction type with the Reaction type list (Figure 2-1).

Figure 2-1: After adding a Reaction node, enter the chemical reaction formula and
specify the reaction type.

Right-click any Reaction node to disable and enable the corresponding node in the
Model Builder. Creating reaction subsets in this way is a straightforward approach to
investigate the influence of individual reactions on the overall reaction system. Species
that take part only in deactivated reactions are automatically deactivated, as indicated
by the unavailable Species feature nodes. If a reaction is deleted, the interface
automatically deletes those species that take part only in the deleted reactions.

ABOUT REACTION IDENTIFICATION NUMBERS, VARIABLE SCOPE, AND

LABELING
When chemical formulas are entered, each reaction is associated with a unique ID
(identification) number (Figure 2-2). The ID number is not a row number but rather
an absolute reference number to a given reaction. This means that a reaction keeps its
ID number, even if reactions are deleted with a lower number. Furthermore, constants
and expressions within fields associated with a given reaction are also indexed with the
reaction number.

28 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

The Name prepended to the variable name is called the variable scope. Defaults are re
and chem for the Reaction Engineering and Chemistry interface, respectively. All
variables set up by the interface are given the same scope. The variable scope can be
useful to couple the equations of different physics interfaces.

Name/Variable scope

ID number

Figure 2-2: The ID number of each Reaction node is displayed in front of the reaction
formula.

As a general labeling rule, the variable name that refers to the contents of a field
associated with a Reaction node is given by the physics interface Name, followed by the
field name, and ends with the reaction ID number. For example, the contents of the
reaction rate field r for Reaction 1 is assigned the variable name re.r_1.

For an example of how to use variables with scope, see Tank Series with
Feedback Control: Application Library path
Chemical_Reaction_Engineering_Module/Ideal_Tank_Reactors/
tankinseries_control

OVERVIEW OF THE REACTION ENGINEERING AND CHEMISTRY INTERFACES | 29

 Using the Species Node
The Reaction Engineering Interface and The Chemistry Interface generate Species
nodes in the Model Builder based on the chemical reaction formulas entered in the
Settings window for Reaction.

Figure 2-3: Species nodes are generated automatically as chemical reaction formulas are
entered in the Reaction nodes.

As with Reaction features you can add, remove, or deactivate Species features by
right-clicking a node in the Model Builder. Deactivation of a species automatically
deactivates any reactions in which the species is participating.

In the Reaction Rate section it is possible to alter the definition of the reaction rate of
the species. This will override the settings in the Reaction feature, where the rate is
defined by the stoichiometry of the reaction(s) in which the species participates.

It is also possible to add individual Species nodes with either reactive or non-reactive
species.

30 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

CHOOSING THE SPECIES TYPE
For each species entered, it is possible to change its characteristics by selecting its
Species type—Bulk species, Surface species, or Solvent.

The Species type selection has implications in the calculation of thermodynamic and
transport properties.

Bulk species and Surface species, defined per reactor volume and area, respectively, set
the mixture’s physical properties dependent upon its composition. However,
configuring a species as a Solvent sets the physical properties of the reacting fluid
mixture equal to those of the solvent species; specifically, its density, heat capacity,
viscosity, and thermal conductivity. The interface also implements a solute-solvent
approximation for the interaction of species in the fluid and describes the transport
properties accordingly. In material balances this means that the diffusion coefficient is
independent of any of the solute’s concentrations, because every solute only interacts
with solvent molecules, regardless of the concentration. In addition, the convective
term in the flux of species is directly given by the velocity field of the solvent multiplied
by the solute concentration.

The Species type has implications on the Generate Space-Dependent Model procedure
since it determines whether interfaces using a solvent-solute approximation of the
reacting fluid mixture (as in The Transport of Diluted Species Interface) or a full
multicomponent description of the reacting fluid mixture (as in The Transport of
Concentrated Species Interface) should be generated.

Furthermore, the Species type affects the reaction kinetics. Solvent sets the species’
concentration to a constant value (the initial species concentration). The Reacting
Engineering interface does not formulate a mass balance for the solvent species. This
setting corresponds to situations where the solvent does not take part in chemical
reactions at all, or where it reacts but is present in large excess.

CREATING VALID SPECIES NAMES AND LABELING

Valid species names consist of a case-sensitive combination of letters, numbers, and “+”
or “−” signs. With the exception of the “+” and “−” signs, which are used for ions,
special characters are not allowed as species names or part of species names (for
example, (), [], *, #, and _). In addition, the first character in a species name must be
a letter to avoid confusion with the stoichiometric coefficients in the reaction formula.
Ions are labeled with one plus or minus sign per species charge added directly after the
species name. For example, A++ represents a cationic monomer with a double positive
charge; A2+ represents a cationic dimer of species A with a single positive charge; and
2A+ represents two cationic monomers, each with a single positive charge. This

OVERVIEW OF THE REACTION ENGINEERING AND CHEMISTRY INTERFACES | 31

 automatically fills in the charge of the species ion the Charge field in the associated
Species feature.

Furthermore, it applies that adding (ads) directly after the species name creates a
surface species named speciesname_surf. Additionally, adding (s), (l), or (g) creates
either a solid, liquid, or gaseous species denoted speciesname_solid,
speciesname_liquid speciesname_gas, respectively. Note that the fluid Mixture,
gas or liquid, remains the same despite the presence of any of these species in the
system.

Similar to the labeling rule applying to Reaction nodes, the variable name referring to
the contents of a field associated with a Species node is given by the interface Name,
followed by the field name, and ending with the species name. For example, the
contents of the Rate expression field R for the species roh is assigned the variable name
re.R_roh (for the Reaction Engineering interface). Access the definition of all the
variables used by a specific node by displaying the Equation View node. To display the
node, click the Show button ( ) and select Equation View.

• Theory for the Reaction Engineering and Chemistry Interfaces

• Variable Naming Convention and Namespace

Using the Equation View Node - Reactions and Species

To display the Equation View node, click the Show button ( ) and select Equation
View. Expand any node, for example the Reaction or Species nodes, and click the
Equation View node to see the page where the definition of all the variables used by a
specific node are listed (Figure 2-4).

32 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

Figure 2-4: The definition of variables used by a node are accessible through the Equation
View.

OVERVIEW OF THE REACTION ENGINEERING AND CHEMISTRY INTERFACES | 33

 Theory for the Reaction Engineering
a nd C he m i s t r y In t erfaces
The Reaction Engineering Interface and The Chemistry Interface theory is described
in this section.

• Reactor Types in the Reaction Engineering Interface

• Transport Properties
• CHEMKIN Data and NASA Polynomials
• Working with Predefined Expressions
• References for the Reaction Engineering Interface

Reaction Kinetics and Rate Expressions

The modeling of reactions in COMSOL is based on the mass action law. Consider a
general reaction belonging to a set of j reactions and involving i species:

f (2-1)
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 (2-2)
i ∈ react i ∈ prod
f r
Here, k j and k j denote the forward and reverse rate constants, respectively. The
concentration of species i is denoted as ci (SI unit: mol/m3). The stoichiometric
coefficients are denoted νij, and are defined as being 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 of reaction

rates can be included by using the predefined Arrhenius expression for the rate
constants:

34 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

 T n
k = A  --------- exp  – -----------
E
(2-3)
 T ref  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 volumetric concentrations).

The default settings for the reaction given by Equation 2-1 and assuming equilibrium,
yields the equilibrium expression in Equation 2-4:

x y
c X c Y ...
K eq = -----------------
a b
- (2-4)
c A c B ...

In the case of reversible reactions, it is also possible to make use of equilibrium

relationships in order to indirectly calculate reaction constants. For example, calculate
the reverse rate constant from the equilibrium condition in this way:

f
r k
k = --------- (2-5)
K eq

The Equilibrium Constant

In general, chemical equilibrium is reached when the Gibbs free energy of the system
is minimized. The Gibbs free energy of is defined as

G ( T, P ) = U + PV – TS = H – TS (2-6)

where U is the internal energy, P is pressure, V is volume, T is temperature, S is

entropy and H is enthalpy of the system. For a closed system

dU = δQ + δW = TdS – PdV (2-7)

where δQ is (reversible) heat transfer to the fluid and δW is (pressure) work in the
system. The change in Gibbs free energy can be written as

dG = TdS – PdV + PdV + VdP – TdS – SdT = VdP – SdT (2-8)

Chemical potential μi is defined as partial molar Gibbs energy for species

THEORY FOR THE REACTION ENGINEERING AND CHEMISTRY INTERFACES | 35

 ∂G 
μ i =  (2-9)
∂ n i T, P, ni ≠ nj

where n is the number of mole of species i in the system. At constant temperature, this
expression can be integrated as a function of pressure

μi
μ dμ = P v̂i dP
Pi
° °
(2-10)
i

o
where v is molar volume and μ i is chemical potential of species at standard state. For
an ideal gas this can be expressed as

o  Pi 
μ i – μ i = RT ln  -----o- (2-11)
P 

The equilibrium criterion can be written as

 νi μi = 0 (2-12)
i

where νi is the stoichiometric number and μi is the chemical potential of species i in

the reaction. We can evaluate the chemical potential as partial molar Gibbs energy of
species in mixture as

o  fˆi 
μ i – μ i = RT ln  ----o- (2-13)
f i 

where fˆi is the fugacity of species i in the mixture, and f i is the fugacity of pure species
o

in the standard state. Equation 2-12 can be rewritten as

 fˆi  ν i

o
ν i μ i + RT ln ∏  ----o- = 0
f i 
(2-14)
i i

The equilibrium constant for the reaction, K, is defined as

 – ΔG orxn νi  fˆi  ν i
K ( T ) = exp  -------------------- =
 RT  ∏ ai = ∏  ----f o- (2-15)
i i i

where ai is the activity of species in the system.

36 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

 o
ΔG rxn is the Gibbs free energy of reaction (including formation terms) which is
defined, in accordance with Equation 2-6, as

o o o
ΔG rxn = ΔH rxn – T ΔS rxn (2-16)
o o
the enthalpy of reaction, ΔH rxn , and entropy of reaction, ΔS rxn , both at a given
temperature T is defined as

 T 
 νi  ΔH f, i + T Cp, i dT
o o
ΔH rxn ( T ) = (2-17)
o
i

 T C p, i 
 νi  Sabs, i + T ----------
o
ΔS rxn ( T ) = - dT (2-18)
T o

i
o o
Here T is the temperature at standard state. ΔH f, i and S abs, i are the standard
enthalpy of formation and absolute entropy for each species (these data are available in
the COMSOL database).

ACTIVITY
Activity of species, ai is defined by Equation 2-13 as

o
 μi – μi 
a i = exp  ----------------- (2-19)
 RT 

Activity depends on the choice of an arbitrary standard state. The standard state of
pure species is usually at 105 Pa and for solute in solution is based on hypothetical
molality or amount concentration also referred as infinite dilute behavior.

Activity of species in a mixture is expressed by relationship between dimensionless

activity coefficients, γi, and measured amount of species in the system.

ci
a i = γ x, i x i = γ c, i --------- (2-20)
c ref

Activity coefficients is usually estimated by Activity coefficient models.

Gas phase
The standard state is the pure species at ideal gas condition, 1 atm and the equilibrium
temperature. Activity of species in mixture is expressed by:

THEORY FOR THE REACTION ENGINEERING AND CHEMISTRY INTERFACES | 37

 fˆ i y i φ̂ i P
a i = ----o- = -------------
o
- (2-21)
fi P

where fˆ i and φ̂ i are fugacity and fugacity coefficient of species i in the mixture.

Liquid phase
The standard state is pure liquid species at 1 atm and equilibrium temperature. The
fugacity of a species in a mixture is given by

fˆ i = y i γ i f i (2-22)

where γi is the activity coefficient of species in the mixture and fi is the fugacity of pure
species at the equilibrium temperature and pressure. The activity is expressed by

yi γi fi
a i = ------------
o
- (2-23)
fi

where fio is the fugacity of pure species at the equilibrium temperature and 1 atm. The
o
ratio f i ⁄ f i is given by

f v̂ i
----i = exp  -------- ( P – P i )
sat
(2-24)
o  RT 
fi

where v̂ i is the partial molar volume of species and Psat is species saturated vapor
pressure. For liquids is weak function of pressure and can be assumed to be 1 unless at
high pressure.

Dilute Solutions
The concentration can in the case of non-ideal mixtures be replaced with the activity.
In these interfaces, the dimensionless activity (ai) depend on species concentration (ci),
activity coefficient (γi) and the standard state concentration (c0s=1 mol/m3).

ci
a i = ------- γ i (2-25)
c 0s

Additionally, an effective species concentration (ce,i) (SI unit: mol/m3) is used in the
reaction rates (Equation 2-2) when activities are utilized.

c e, i = c i γ i = a i c 0s (2-26)

38 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

AUTOMATICALLY DEFINED EQUILIBRIUM CONSTANTS
Below the automatically defined equilibrium constants are defined in terms of the
equilibrium expression Keq

ν
∏ ci i
νi i ∈ prod
K eq = ∏ ci = --------------------------
–ν
(2-27)
i ∏ ci i
i ∈ react

Gas Phase
Inserting Equation 2-21 in Equation 2-15 gives:

 φ̂ i P  ν i
K ( T ) = K eq ∏  -----------------o-
 c sum P 
(2-28)
i

where for ideal mixtures, the fugacity coefficients φ̂ i are equal to 1.

Liquid Phase
For low and moderate pressure, the equilibrium constant can be reformulated by
substitution of Equation 2-23 to Equation 2-15 as:

γi νi
K ( T ) = K eq ∏  ----------
c sum
- (2-29)
i

Handling of Equilibrium Reactions

EXAMPLE I
The following short example illustrates how the Reaction Engineering interface and
the Chemistry interface handle equilibrium reactions in the formulation of the material
balance equations.

Consider the reaction:

f (2-30)
k
A r B
k

According to Equation 2-2 the reaction rate (SI unit: mol/(m3·s)) is formulated as:

f r
r = k cA – k cB

THEORY FOR THE REACTION ENGINEERING AND CHEMISTRY INTERFACES | 39

 where cA and cB (SI unit: mol/m3) are the concentrations of A and B, and kf and kr
(SI unit: 1/s) are the forward and reverse rate constants, respectively. The net rate
expressions with respect to species A and B are then:

f r
RA = – k cA + k cB = –r

f r
RB = k cA – k cB = r

Assuming the reaction in Equation 2-30 is at equilibrium, the reaction rate r is 0:

f r
r = k cA – k cB = 0

The relationship between the forward and reverse reaction rates in Equation 2-30 is
given by the following ratio:

f cB
eq k
K = ----r- = ------ (2-31)
k cA

The Reaction Engineering interface also sets up mass balances that are solved. The
general material balances for species A and B, respectively, are:

∂c A
= RA = –r (2-32)
∂t

∂c B
= RB = r (2-33)
∂t

The rate of consumption of species A equals the production rate of species B, as shown
in Equation 2-32 and Equation 2-33.

With the combined information in Equation 2-32, Equation 2-33, and

Equation 2-31, the Reaction Engineering interface is able to define the mass balances
for the equilibrium system without the reaction rate expressions. The equation system
solved for becomes:

∂ (c + c ) = 0
(2-34)
∂t A B

eq cB
K = ------ (2-35)
cA

40 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

In general, for a system of reactions contributing to k mass balances and with j
reactions being at equilibrium, the reduced system of equations to be solved is
composed of k – j mass balances and j equilibrium expressions. The elimination
process producing the above system of equations is automated, allowing simple
modeling of chemical equilibrium reactions together with irreversible and/or
reversible reactions.

EXAMPLE II
This example shows how equilibrium reactions are considered in the Reaction
Engineering interface using the Equilibrium Species Vector section.

If two non-equilibrium reactions are taking place in a perfectly mixed isothermal

reactor of constant volume:

f
k1
A B

f (2-36)
k2
B 2C
k2r

the corresponding mass balances are:

d-
----- c = –r1 (2-37)
dt A

d-
----- c = r1 – r2 (2-38)
dt B

d-
----- c = 2r 2 (2-39)
dt C

Now compare Equation 2-37, Equation 2-38, and Equation 2-39 with the balance
equations that the physics interface sets up for the related chemistry, where the second
reaction is instead an equilibrium reaction:

f (2-40)
k1
A B

K2
eq (2-41)
B 2C

THEORY FOR THE REACTION ENGINEERING AND CHEMISTRY INTERFACES | 41

 In contrast to the reversible reaction given by Equation 2-36, to make use of the
information contained in the equilibrium relation, the mass balances must be
reformulated. Mass balances set up for the reactions given by Equation 2-40 and
Equation 2-41 are then:

d-
----- c = –r1
dt A

d-
----- ( 2c B + c C ) = 2r 1 (2-42)
dt

2
eq cC
K 2 = ------ (2-43)
cB

The equilibrium expression (Equation 2-43) introduces an algebraic relationship

between the species’ concentrations.

Two species, B or C, can be set as Predefined Dependent Species in the Equilibrium

Species Vector section. Selecting B as the dependent species solves Equation 2-42 for
the concentration of C, while B is computed from Equation 2-43.

Reactor Types in the Reaction Engineering Interface

MASS BALANCE
The mass balances that are set up in the Reaction Engineering interface are simplified
versions of the general mass transport equation. The main assumption is that the
reactor is perfectly mixed, meaning that any variations in compositions within the
reactor are neglected.

• Mass Balance Equation

42 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

ENERGY BALANCE
The energy balances solved in the Reaction Engineering interface are derived from the
general energy balance of a system. The utilized equation follows the perfect mixing
assumption and is dependent on the selected reactor as described below.

Theory for Heat Transfer

The following reactor types are available in the Reaction Engineering interface (the
Chemistry interfaces does not contain reactor models):

• Batch • CSTR, Constant Volume

• Batch, Constant Volume • Semibatch
• CSTR, Constant Mass/Generic • Plug Flow

BATCH
In the batch reactor no mass enters or leaves the system. Common for all reactor
models is that reacting fluids in the gas phase are assumed to behave as ideal gases.
Liquid mixtures are assumed to be ideal and incompressible.

The species mass balances are given by:

d ( ci Vr )
-------------------
- = Vr Ri (2-44)
dt

which takes into account the effect of changing volume. In Equation 2-44, ci (SI unit:
mol/m3) is the species molar concentration, Vr (SI unit: m3) denotes the reactor
volume, and Ri (SI unit: mol/(m3·s)) is the species rate expression.

For an ideal reacting gas, the energy balance is:

THEORY FOR THE REACTION ENGINEERING AND CHEMISTRY INTERFACES | 43

 dT dp
Vr  ci Cp, i -------
dt
- = Q + Q ext + V r -------
dt
(2-45)
i

In Equation 2-45, Cp,i (SI unit: J/(mol·K)) is the species molar heat capacity, T (SI
unit: K) is the temperature, and p (SI unit: Pa) the pressure. On the right-hand side,
Q (SI unit: J/s) is the heat due to chemical reaction, and Qext (SI unit: J/s) denotes
heat added to the system. The heat of reaction is:

Q = –Vr  Hj rj
j

where Hj (SI unit: J/mol) is the enthalpy of reaction, and rj (SI unit: mol/(m3·s)) the
reaction rate.

For an incompressible and ideally mixed reacting liquid, the energy balance is:

dT
Vr  ci Cp, i -------
dt
- = Q + Q ext (2-46)
i

Ibuprofen Synthesis: Application Library path

Chemical_Reaction_Engineering_Module/Ideal_Tank_Reactors/
ibuprofen_synthesis

BATCH, CONSTANT VOLUME

The constant volume batch reactor is the default reactor. It assumes a closed, perfectly
mixed system of constant volume. The species mass balances are:

dc i
-------- = R i
dt

For an ideal reacting gas, the energy balance is given by Equation 2-45. For an
incompressible and ideally mixed reacting liquid, the energy balance is given by
Equation 2-46.

Neutralization of Chlorine in a Scrubber: Application Library path

Chemical_Reaction_Engineering_Module/Ideal_Tank_Reactors/
chlorine_scrubber

44 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

CSTR, CONSTANT MASS/GENERIC
The continuous stirred tank reactor (CSTR) has reacting species entering and leaving
the reactor by means of inlet and outlet streams. The reactor is again assumed to be
perfectly mixed, so that the species concentrations of the exit stream are the same as
the concentrations in the reactor volume.

The species mass balances for the CSTR are given by:

d ( ci Vr )
-------------------
dt
- =
 vf, m cf, m – vci + Ri Vr (2-47)
m

In Equation 2-47, cf,m (SI unit: mol/m3) is the species molar concentration of the
associated feed inlet stream vf,m (SI unit: m3/s). Vr (SI unit: m3) denotes the reactor
volume and is a function of time.

The reactor volume as a function of time is given by:

dV
---------r- =
dt  v f, m – v + v p (2-48)
m

In Equation 2-48, vp (SI unit: m3/s) denotes the volumetric production rate. It is
given by Equation 2-49 for ideally mixed liquids and by Equation 2-50 for ideal gases.

Ri Mi
vp = Vr  -------------
ρi
-, Ri =  νij rj (2-49)
i j

Rg T
v p = ----------- V r
p  Ri (2-50)
i

where νij is the stoichiometric coefficient of species i in reaction j, Mi (SI unit: kg/
mol) denotes the species molecular weight, ρi (SI unit: kg/m3) the species density, and
Ri (SI unit: mol/(m3·s)) is the reaction rate of species i.

THEORY FOR THE REACTION ENGINEERING AND CHEMISTRY INTERFACES | 45

 When this reactor model is solved for constant mass, the reactor model assumes that
the volumetric flow rate of the outlet stream, v (SI unit: m3/s), is adjusted in such a
way that the total mass of the reactor is held constant:

 v f, m ρ f, m
m
v = ------------------------------
- (2-51)
ρ

In contrast, when the model is set to be solved for generic conditions a specific outlet
flow stream can be set.

The energy balance for an ideal reacting gas is:

dT dp
Vr  ci Cp, i -------
dt
- = Q + Q ext + V r ------- +
dt   vf, mi cf, mi ( hf, mi – hi ) (2-52)
i m i

For an incompressible and ideally mixed reacting liquid, the energy balance is:

dT
Vr  ci Cp, i -------
dt
- = Q + Q ext +   vf, mi cf, mi ( hf, mi – hi ) (2-53)
i m i

Ideal Stirred Tank Reactor System: Application Library path

Chemical_Reaction_Engineering_Module/Ideal_Tank_Reactors/
tank_flow_system

CSTR, CONSTANT VOLUME

This reactor type is a CSTR reactor where the reactor volume is constant.

The species mass balances are given by:

d ( ci Vr )
-------------------- =
dt  vf, m cf, m – vci + Ri Vr (2-54)
m

Assuming constant reactor volume:

dV
---------r- = 0
dt

and setting the volumetric outlet rate to:

46 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

 v =  v f, m + v p (2-55)
m

Equation 2-54 can be rewritten as:

dc i
V r -------- = v f, i c f, i –   vf, i + vp ci + Ri Vr (2-56)
dt

The volumetric production rate, vp, is defined as in Equation 2-49 and Equation 2-50.

The energy balance is the same as for the CSTR with Constant Mass/Generic reactor
type (Equation 2-53).

Startup of a Continuous Stirred Tank Reactor: Application Library

path Chemical_Reaction_Engineering_Module/Tutorials/cstr_startup

SEMIBATCH
In the semibatch reactor, reactants enter the reactor by means of one or several feed
inlet streams.

The species mass balances are given by:

d ( ci Vr )
-------------------
- = v f, i c f, i + R V r (2-57)
dt i

The reactor volume is a function of time given by:

dV
---------r- =
dt  vf, m + vp (2-58)
m

THEORY FOR THE REACTION ENGINEERING AND CHEMISTRY INTERFACES | 47

 The volumetric production rate, vp, is defined as in Equation 2-49 and Equation 2-50.

An energy balance over the Semibatch reactor results in the same energy balance
expression as for the CSTR reactor types (Equation 2-53).

Semibatch Polymerization: Application Library path

Chemical_Reaction_Engineering_Module/Ideal_Tank_Reactors/
semibatch_polymerization

PLUG FLOW
In the plug flow reactor the species concentrations and the temperature vary with
position. For a tubular reactor configuration, plug flow assumes concentration and
temperature gradients to only develop in the axial direction but not in the radial
direction of the reactor.

The species mass balances are given by:

dF
---------i = R i (2-59)
dV

where Fi (SI unit: mol/s) is the species molar flow, V (SI unit: m3) is the reactor
volume, and Ri (SI unit: mol/(m3·s)) denotes the species rate expression.

In order to evaluate the rate expressions Ri, which are functions of the species
concentrations, the physics interface calculates:

Fi
c i = -----
v

where v (SI unit: m3/s) is the volumetric flow rate.

For liquids, the volumetric flow rate is given by:

48 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

 Fi Mi
v =  ------------
ρi
-
i

where Mi (SI unit: kg/mol) denotes the species molecular weight and ρi (SI unit: kg/
m3) the species density

For ideal gases:

Rg T
v = -----------
p  Fi
i

so that

p Fi
c i = ----------- -------------
Rg T
 Fi
i

where p (SI unit: Pa) is the constant pressure.

Neglecting pressure drop, the energy balance for an ideal reacting gas, as well as an
incompressible and ideally mixed reacting liquid is given by:

dT
 Fi Cp, i -------
dV
- = Q + Q ext (2-60)
i

Equation 2-60 is similar to the energy balance for the batch reactors (Equation 2-46),
but with a reactor volume dependence instead of a time dependence.

Nonisothermal Plug Flow Reactor: Application Library path

Chemical_Reaction_Engineering_Module/Tutorials/nonisothermal_plug_flow

Transport Properties
The Reaction Engineering Interface and The Chemistry Interface can calculate several
transport properties that can be accessed in interfaces in space dependent models.

DIFFUSIVITY
The diffusivity is calculated in terms of binary diffusion coefficients. These are available
for the following fluid mixtures:

THEORY FOR THE REACTION ENGINEERING AND CHEMISTRY INTERFACES | 49

 Gases with or without Solvent
The diffusion coefficients are calculated from the following expression based on kinetic
gas theory:

3 3
– 22 T ( M A + M B ) ⁄ ( 2 ⋅ 10 M A M B ) –1
D AB = 2.6628 ⋅ 10 ⋅ -------------------------------------------------------------------------------------- ⋅ Ω D (2-61)
pσ A σ B

Here, DAB (SI unit: m2/s) is the binary diffusion coefficient, M (SI unit: kg/mol)
equals the molecular weight, T (SI unit: K) represents the temperature, p (SI unit: Pa)
is the pressure, and σ (SI unit: m) equals the characteristic length of the
Lennard-Jones/ Stockmayer potential. In addition, ΩD is the collision integral, given
by the following equation (Ref. 6 and Ref. 7):

–c2
ΩD = c1 ( T ⁄ εk ) + c 3 [ exp ( – c 4 T ⁄ ε k ) ] + c 5 [ exp ( – c 6 T ⁄ ε k ) ]
– 40 2 2 (2-62)
( 4.748 ⋅ 10 )μ D, A μ D, B
+ c 7 [ exp ( – c 8 T ⁄ ε k ) ] + ----------------------------------------------------------------
2 3 3
-
k b Tε k σ A σ B

where

εA εB
εk = ------------ (2-63)
2
kb

In Equation 2-62, cx are empirical constants, μD is the species dipole moment value
(SI unit: Cm) and ε/kb (SI unit: K) the potential energy minimum value divided by
Boltzmann’s constant. Tabulated data in literature frequently lists values of ε/kb rather
than ε. It should be noted that predefined expressions for binary diffusivities only treat
ideal gas mixtures. Thus, these are applicable as input only for gases at moderate
pressure in multicomponent diffusive transport models.

The binary diffusivity according to Equation 2-61 is also suited for gaseous species in
solvent, simply by setting either the component A or B to the solvent. The binary
diffusion coefficient is in this case equal to the diffusion coefficient of the bulk species.

Liquid with Solvent

The diffusivity of a species A in a solvent B is calculated with the Wilke-Chang
equation (Ref. 8):

1⁄2
– 15 ( φ B M B ) T
D AB = 3.7·10 ---------------------------------
- (2-64)
0.6
μ B V b, A

50 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

where μB (SI unit: N·s/m2) denotes the solvent’s dynamic viscosity (see
Equation 2-69), and Vb,A (SI unit: m3/mol) equals the molar volume at the normal
boiling point of the solute species. φ B is the dimensionless association factor of the
solvent, which by default is set to 1.

DYNAMIC VISCOSITY
The dynamic viscosities are computed for the following fluid mixtures:

Gases with Solvent

The dynamic viscosity of the mixture is assumed to be the same as that of the solvent.
This is given by the kinetic gas theory (Ref. 6 and Ref. 7), with species i being the
solvent:

3
T ( M i ⋅ 10 )
– 6 ---------------------------------- –1
μ = 2.669 ⋅ 10 2
ΩD (2-65)
σi

In Equation 2-65, μ (SI unit: Ns/m2) represents the dynamic viscosity, and ΩD is the
dimensionless collision integral given by:

–b2
ΩD = b1 ( T ⁄ ( εi ⁄ kb ) ) + b 3 [ exp ( – b 4 T ⁄ ( ε i ⁄ k b ) ) ]
– 40 4 (2-66)
( 4.998 ⋅ 10 )μ D, i
+ b 5 [ exp ( – b 6 T ⁄ ( ε i ⁄ k b ) ) ] + -------------------------------------------------
2 6
-
k b T ( ε i ⁄ k b )σ i

In Equation 2-65 and Equation 2-66, bx are empirical constants, μD (SI unit: Cm) the
species dipole moment value, and ε/kb (SI unit: K) the potential energy minimum
value divided by Boltzmann’s constant. Tabulated data in literature frequently lists
values of ε/kb rather than ε, and σ (SI unit: Å) is the characteristic length value.

Gases without Solvent

The dynamic viscosity of gas mixtures without solvent are calculated according to
Ref. 9 with the following expression:

 
 n

 μ 
 --------------------------------------------
-

i
μ = (2-67)
 j=n 
i = 1 1 
 1 + ----
 x i
 x j φ ij

j=1, j ≠ i

where φij is defined as:

THEORY FOR THE REACTION ENGINEERING AND CHEMISTRY INTERFACES | 51

 0.5 0.25 2
[ 1 + ( μi ⁄ μj ) ( Mj ⁄ Mi ) ]
φ ij = ----------------------------------------------------------------------------
0.5
(2-68)
( 2 2 ) [ 1 + Mi ⁄ Mj ]

In Equation 2-67 and Equation 2-68, xi is the molar composition and μi is computed
with Equation 2-65 for each of the species in the mixture.

Liquid with Solvent

The dynamic viscosity of the mixture is assumed to the same as that of the solvent. An
approximate expression for the temperature dependence of the dynamic viscosity is
given by (Ref. 10):

– 3 .758
3 – 0.2661 T – T ref
μ = 10  ( μ ref 10 )
–3
+ -------------------- (2-69)
 223

where μ (SI unit: Ns/m2) is the dynamic viscosity. As inputs for Equation 2-69, the
physics interface takes the reference viscosity, μref (SI unit: Pa⋅s) at the reference
temperature Tref (SI unit: K).

THERMAL CONDUCTIVITY
The thermal conductivity is calculated as well for some types of fluid mixtures:

Gas With or Without Solvent

The predefined expression for thermal conductivity comes from the Stiel-Thodos
equation (Ref. 11), which is defined as:

μ
k = ----- ( 1.15C p + 0.88R g ) (2-70)
M

where k (SI unit: W/(m·K)) is the thermal conductivity and Cp (SI unit: J/(mol·K))
denotes the molar heat capacity. Equation 2-70 is a function of viscosity, μ, as given by
Equation 2-65. Equation 2-70 is directly used in the case of a solvent; all parameters
being those of the solvent. Without a solvent, however, the following equation is also
used:

1  x i – 1
k = ---
2  xi ki +   ----k-i
i=1 i=1

where ki is the thermal conductivity of each species i and xi the molar composition for
each of the species in the mixture.

52 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

CHEMKIN Data and NASA Polynomials
CHEMKIN® files can be used to import data for simulation of complex chemical
reactions in the gas phase. These input files may contain three basic sets of
information—chemical kinetics, species thermodynamic properties, and species
transport properties for either volumetric or surface species. Use imported data to set
up and do the following:

• Solve mass and energy balances for ideal reactor systems ( reactors, semi- reactors,
CSTRs, and plug flow reactors).
• Evaluate species transport properties as a function of reactor conditions.
• Evaluate mass, energy, and momentum balances for space-dependent models, and
transfer them to COMSOL Multiphysics.

It is possible to read the input files for kinetics, thermodynamic, and transport
properties independently and use these as separate data resources. For example, if a set
of reactions is entered into the Reaction Engineering interface, species thermodynamic
and transport data can be supplied by reading the appropriate input files. The full
functionality of the physics interface is retained even after the import procedure. This
means that all expressions and all data imported into the software are available for
reference and for editing.

The following CHEMKIN files are compatible:

• Transport CHEMKIN files that supply data used to compute Transport Properties.
• Thermodynamic CHEMKIN files containing data for Gordon and McBride or
NASA polynomials (Ref. 4). These polynomials are denoted NASA format and
compute the species’ heat capacity, Cp, molar enthalpy, h, and molar entropy, s:
2 3 4
C p, i = R g ( a 1 + a 2 T + a 3 T + a 4 T + a 5 T ) (2-71)

a2 2 a3 3 a4 4 a5 5
h i = R g  a 1 T + ------ T + ------ T + ------ T + ------ T + a 6 (2-72)
 2 3 4 5 

a3 2 a4 3 a5 4
s i = R g  a 1 ln T + a 2 T + ------ T + ------ T + ------ T + a 7 (2-73)
 2 3 4 

THEORY FOR THE REACTION ENGINEERING AND CHEMISTRY INTERFACES | 53

 Here:

- Cp,i (SI unit: J/(mol·K)) denotes the species’ molar heat capacity,
- T (SI unit: K) is the temperature,
- Rg the ideal gas constant, 8.314 J/(mol·K),
- hi (SI unit: J/mol) is the species’ molar enthalpy, and
- si (SI unit: J/(mol·K)) represents its molar entropy at standard state.
From the CHEMKIN files the coefficients a1 to a7 are directly imported into the
corresponding NASA format fields. Coefficients for NASA polynomials are available as
public resources (Ref. 12).

Kinetics CHEMKIN files that can be imported in the Reversible Reaction Group
feature. These consist of reaction kinetics data, such as activation energy (SI unit: J/
mol).

Homogeneous Charge Compression Ignition of Methane: Application

Library path Chemical_Reaction_Engineering_Module/Ideal_Tank_Reactors/
compression_ignition

NOx Reduction in a Monolithic Reactor: Application Library path

Chemical_Reaction_Engineering_Module/Tutorials/monolith_3d

Chemical Vapor Deposition of GaAs: Application Library path

Chemical_Reaction_Engineering_Module/
Reactors_with_Mass_and_Heat_Transfer/gaas_cvd

Working with Predefined Expressions

You can choose whether to use the predefined expressions as given, use parts of a
predefined set of expressions, or replace expressions entirely. A few short examples
highlight the use of the predefined expressions used in the Species Transport
Expressions and Species Thermodynamic Expressions sections to enter the
thermodynamic properties of carbon monoxide. The sections also illustrate the
possibility to adapt to different modeling situations.

CASE 1
Carbon monoxide is part of a reacting mixture. You want to do several things: make
use of the predefined expressions of species Cp as an input to the heat capacity of the
reacting mixture (Equation 2-71); use the predefined expression h for each species to

54 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

calculate the heat of reaction (Equation 2-72); and use the predefined expression s for
each species to calculate the entropy of reaction (Equation 2-73) and subsequently the
equilibrium constant of reaction (See Handling of Equilibrium Reactions).

To accomplish this, enter the seven coefficients of the NASA format, a1 to a7, into the
appropriate fields, or import a CHEMKIN Import for Species Property thermo input
file.

CASE 2
Carbon monoxide is part of a reacting mixture. You want to make use of the
predefined expressions of species Cp to calculate the heat capacity of the reacting
mixture (Equation 2-98).

Polynomials for Cp are available in the literature (Ref. 2, Ref. 3, and Ref. 5) in the
frequently used form

 an T
n–1
Cp = Rg n = 1, …, 5
n

You can directly use the predefined expression for the species’ heat capacity,
Equation 2-71, also given in the Cp field, by supplying coefficients in the a1 to a5 fields.

You also want to use the predefined expressions h for each species to calculate the heat
of reaction (Equation 2-72). An option is to make use of the heat of formation at
standard state (298.15 K) to calculate the coefficient a6. Identifying the coefficient a6
of Equation 2-72 is straightforward. In the NASA polynomial format, the species
molar enthalpy is related to its heat capacity according to

T
h = 0 Cp dT + h ( 0 ) (2-74)

Inserting Equation 2-71 into Equation 2-74, and comparing the result with
Equation 2-72, shows that the term a6 Rg is identified as the species enthalpy of
formation at 0 K, that is, h(0). Evaluate h(0) from the species enthalpy of formation
at standard state temperature, Tstd = 298.15 K, which is given by

h ( T std ) a2 2 a3 3 a4 4 a5 5
a 6 = -------------------- –  a 1 T std + ------ T std + ------ T std + ------ T std + ------ T std (2-75)
Rg  2 3 4 5 

THEORY FOR THE REACTION ENGINEERING AND CHEMISTRY INTERFACES | 55

 CASE 3
Carbon monoxide is again part of a reacting mixture. It is satisfactory to approximate
Cp as being constant. Specify the species enthalpy by making use of the heat of
formation at 298 K, h(298), according to the well-known expression

h = C p ( T – 298 ) + h ( 298 )

References for the Reaction Engineering Interface

1. H.G. Rackett, “Equation of State for Saturated Liquids,” J. Chem. Eng. Data, vol.
15, no. 4, pp. 514–517, 1970.

2. R.H. Perry and D.W. Green, Perry’s Chemical Engineering Handbook, 7th ed.,
McGraw Hill, 1997.

3. B.E. Poling, J.M. Prausnitz, and J.P. O’Connell, The Properties of Gases and
Liquids, 5th ed., McGraw Hill, 2000.

4. S. Gordon and B.J. McBride, Computer Program for Calculation of Complex

Chemical Equilibrium Compositions, Rocket Performance, Incident and Reflected
Shocks, and Chapman-Jouquet Detonations, NASA-SP-273, 1971.

5. M. Zabransky, V. Ruzicka Jr., V. Majer, and E.S. Dolmaski, “Heat Capacity of

Liquids: Critical Review and Recommended Values,” J. Phys. Chem. Ref. Data
Volume I and II, Monograph, No. 6, 1996.

6. P.D. Neufeld, A.R. Janzen, and R.A. Aziz, “Empirical Equations to Calculate 16 of
the Transport Collision Integrals Ω(l,s)*for the Lennard-Jones (12-6) Potential,” J.
Chem. Phys., vol. 57, pp. 1100–1102, 1972.

7. R.S. Brokaw, “Predicting Transport Properties of Dilute Gases,” Ind. Eng. Process
Design Develop., vol. 8, no. 2, pp. 240–253, 1969.

8. C.R. Wilke and P. Chang, “Correlation of Diffusion Coefficients in Dilute

Solutions,” AIChE J., vol. 1, no. 2, pp. 264–270, 1955.

9. C. R. Wilke, “A Viscosity Equation for Gas Mixtures,” J. Chem. Phys., vol. 18, no.
4, pp. 517–519, 1950.

10. W.R. Gambill, “Fused Salt Thermal Conductivity,” Chem. Eng., vol. 66, p. 129,
1959.

11. L.I. Stiel and G. Thodos, “The Viscosity of Polar Substances in the Dense Gaseous
and Liquid Regions,” AIChE J., vol. 10, p. 26–29, 1964.

56 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

12. See, for example, www.comsol.com/chemical-reaction-engineering-module

THEORY FOR THE REACTION ENGINEERING AND CHEMISTRY INTERFACES | 57

 The Reaction Engineering Interface
The Reaction Engineering (re) interface ( ), found under the Chemical Species
Transport branch ( ) when adding a physics interface, is used to model several
chemical reactor types and the evolution of chemical reactions over time. The mass
balance and energy balance equations describing these systems assume perfect or
well-defined mixing in the reactor. Essentially, the physics interface simulates, tank,
and plug flow chemical reactors to investigate the behavior over time of a chemical
reaction.

The reaction kinetics expressions of a reactor can be exported to a space-dependent

model, using the Generate Space-Dependent Model feature. This gives you the power
to simulate reacting systems as they depend on fluid flow, mass transfer, and heat
transfer — in other words, including space dependencies.

Add physics features from the toolbar, or right-click Reaction Engineering to select
features from the context menu. Many of the fields and nodes described in this section
are made available when either a Reaction or a Species (or both) subnode is added to
the Model Builder. Because nodes and subnodes are accessible at any time, and any
change is updated throughout the model, reactions and species are often defined
before the settings described in this section.

All predefined constants and expressions can be overwritten by user-defined

expressions. This makes it possible to go beyond the modeling assumptions that are
the defaults in this physics interface.

• Theory for the Reaction Engineering and Chemistry Interfaces

• Features Nodes Available for the Reaction Engineering Interface

The following is a description of the features and fields available on the Settings
window for Reaction Engineering.

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

58 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

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 setup) is re.

EQUATION
This section displays the governing equations according to the selection of reactor
types in the Reactor Type section.

REACTOR TYPE
Select a Reactor type to define the reaction system. The available reactor types are:
Batch, Batch, constant volume, CSTR, constant volume, CSTR, constant mass/generic,
Semibatch, and Plug flow. Each reactor type solves a mass balance based on properties
typical to the type, such as reactor volume, volumetric production, or flow rate:

• BatchBatch: In reactors no mass enters or leaves the system. This type can account
for a variable reactor volume.
• Batch, Constant Volume: Same as Batch but where the reactor volume is assumed
to be constant. As this is the situation for most reacting systems, this is the default
condition.
• CSTR, Constant Mass/Generic: Continuous stirred tank reactors (CSTR) differ
from batch reactors, since these allow species to enter and leave the reactor by means
of feed inlet streams and outlet streams. The system’s volume is allowed to change,
such as in a car engine cylinder or a balloon. This reactor model can be solved either
for a constant mass condition or by selecting a specific outlet flow.
• CSTR, Constant Volume: Same as the CSTR with constant mass/generic reactor
but assumes that the volume is constant during operation.
• Semibatch: Semibatch reactors differ from batch reactors in that they allow reactants
to enter the reactor by means of one or several feed inlet streams.
• Plug Flow: In the plug flow reactor, the species concentrations and the temperature
vary with position. Plug flow in a tubular configuration means that concentration
and temperature gradients develop only in the axial direction, but not in the radial
direction.

Reactor Types in the Reaction Engineering Interface

THE REACTION ENGINEERING INTERFACE | 59

 ENERGY BALANCE
From the list select to Exclude or Include the energy balance, which in essence
determines whether the system is solved for either isothermal or nonisothermal
conditions, respectively. The latter introduces the temperature as a variable in the
interface.

If Exclude is chosen, enter a Temperature T for the system.

It is possible to incorporate cooling or heating of the reactor. This is done in External

heating or cooling (Qext). Enter a negative value to account for cooling or a positive
one for heating (SI unit: W). Note that for the Plug Flow reactor type, the External
heating or cooling (Q) is defined per reactor volume (SI unit: W/m3).

MIXTURE
Select a Mixture to specify the phase, Gas or Liquid, of the reaction fluid.

Mixture Density
Mixture density always has two settings available: Automatic or User defined. The
mixture density is transferred to physics interfaces set up by the Generate
Space-Dependent Model feature. The density is compiled for both multicomponent
and solute-solvent solutions.

• Automatic selected for Liquid, considers the liquid as ideal and incompressible. The
liquid mixture density depends on the density of i number of pure species (ρi) and
the species mass fraction (wi).
1
ρ = --------------
wi
 ------
ρi
i

The mass fraction is given by the species concentration (ci) and the molar mass (Mi).
ci Mi
w i = --------------------
 ci Mi
i

• Automatic set for Gas calculates the gas mixture density (ρ) from the concentrations
(ci) and molar masses (Mi) of the mixture species, which are automatically taken
from Species features.

60 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

 ρ =  ci Mi (2-76)
i

• If a Species Type is set to Solvent and the Mixture is Liquid, the mixture density is the
same as the solvent density as defined in Density in General parameters in the Species
node. When Mixture is Gas, the mixture density is calculated from Equation 2-76
only for the species set as Solvent.

Reactor Pressure
The Mixture - Gas setting displays the Reactor pressure. For all reactor types, except the
Plug flow reactor, select either a pressure computed from the Ideal gas law or from any
other expression using the User defined option. The Batch and Semibatch reactor types
also have the option to keep the reactor pressure Constant during reaction.

For the Plug Flow reactor, the Reactor pressure can be entered in the case of the Mass
Balance section having the Volumetric rate set to Automatic, in which case the User
defined alternative is available and a constant pressure fits the conditions.

CALCULATE TRANSPORT PROPERTIES

Transport properties are not utilized in the reactor equations available in the Reaction
Engineering interface, where perfect mixing is assumed. However, transport
properties such as diffusivity, thermal conductivity, and viscosity are of central
importance when solving time- and space-dependent models. The physics interface
helps to set up detailed expressions of species transport properties and transfers them
automatically to the multiphysics model through the Generate Space-Dependent
Model feature.

The most general description of a mixture is the one that treats the mixture as a
multicomponent solution, where all species interact with each other. A simplified
description, but still a common one, assumes that the solution has a solvent that
dominates the properties of the solution. The solutes in such a solution interact only
with solvent molecules.

Select the Calculate mixture properties check box to enable calculation of mixture
transport properties exported from the Reaction Engineering interface.

From the list for each property, select the in-built Automatic expression or set a User
defined entry. The mixture properties you can transfer for space-dependent models are:

• Heat capacity (cp) (SI unit: J/(kg·K)) (this is available when the Energy Balance is
set to Include)

THE REACTION ENGINEERING INTERFACE | 61

 • Thermal conductivity (k) (SI unit: W/(m·K))
• Dynamic viscosity (μ) (SI unit: Pa·s) (this is available when a Species Type is set to
Solvent)

• Mixture density (ρ) (SI unit: kg/m3) (this is available under Mixture Density
section)

All species properties needed to compute the mixture properties are entered in the
Species Transport Expression or Species Thermodynamic Expression in the Species node.

Transport Properties

EQUILIBRIUM SPECIES VECTOR

This section is available when the Reaction node incorporates at least one Equilibrium
reaction; Reaction type is set to Equilibrium.

In the Predefined dependent species (separated by ‘,’) text field, edit, if necessary, the
species that depends on the composition of the other species according to the
Equilibrium expression in the Reaction node. To minimize the impact of any numerical
errors, it is recommended to set the species with the highest concentration as
dependent species. The default species is set to the leftmost species in the Reaction
formula.

The Suppress negative concentrations check-box exists to aid the computation of

equilibrium reaction systems. A selected check-box ensures that no negative values of
concentrations are accepted as solution to the equilibrium condition.

Example II in Handling of Equilibrium Reactions.

ACTIVITY
Select the Use activity check box to solve for species activities instead of species
concentrations, which is a common approach when non-ideal fluids are modeled.

62 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

An activity coefficient other than 1 can be set for each species for the Species node in
the Species Concentration/Activity section.

Activity

DISCRETIZATION
The Uniform scaling of concentration variables check box is not selected by default.
When selected, all concentration variables are scaled using the same scale factor in the
Study node. Enabling uniform scaling can decrease solver time for problems involving
many concentration variables.

MASS BALANCE
This section displays the parameters and expressions used in the mass balance equations
for the available reactor types as selected under Reactor type.
TABLE 2-1: REACTOR TYPE PARAMETERS TO DEFINE UNDER MASS BALANCE

REACTOR TYPE PARAMETERS TO DEFINE

Batch Reactor volume Vr

Batch, constant volume Reactor volume Vr
CSTR, constant mass/ Volumetric production rate vp and Volumetric outlet rate v
generic
CSTR, constant volume Volumetric production rate vp and Reactor volume Vr
Semibatch Volumetric production rate vp
Plug flow Volumetric flow rate v

Volumetric Rate
For CSTR, constant volume and Semibatch reactor types, the Volumetric production rate
(vp) is available. For Automatic, the in-built Volumetric production rate expression is
shown. If User defined is selected, the expression can be changed (SI unit: m3/s). For
instance, this enables the setting of zero (0) volumetric production rate, which ignores
volume changes due to reactions.

• For liquid phase reactions, the Automatic expression for the Volumetric production
rate varies with the reaction rate of each species as defined by:

THE REACTION ENGINEERING INTERFACE | 63

 Ri Mi
vp = Vr  -------------
ρi
-, Ri =  νij rj (2-77)
i j

The physics interface automatically inserts the stoichiometric coefficients (νij) and
reaction rate expressions for each species (Ri) that depend on j number of reactions
of a rate (rj), as defined in the Reaction feature node. Furthermore, the values of the
molar mass (Mi) and the species density (ρi) are automatically taken from the
Species features.
• For gas phase reactions, the Automatic expression for the Volumetric production rate
is similarly given by:
Rg T
v p = ----------- V r
p  R i, Ri =  νij rj (2-78)
i j

For CSTR, constant mass/generic, select Volumetric rate to either Constant mass (the
default) or Generic. The Constant mass selection shows both the expression for
Volumetric production rate (vp) (Equation 2-77 or Equation 2-78) and Volumetric
outlet rate (v), the latter is derived from constant mass flow condition through the
reactor:

 vf, m ⋅ ρf, m
m
v = ----------------------------------
- (2-79)
ρ

The mixture density (ρf) of m number of feed inlet streams is determined in the
same way as in the Mixture section. For Generic both the Volumetric rate properties
can be edited (SI unit: m3/s). This means that it is possible to completely control
the volumetric outlet rate from the CSTR.
For the Plug flow reactor, the Volumetric flow rate along the reactor is set. The
Automatic definition computes a variable volumetric flow rate that depends on the
molar flow rate of each species (Fi).
• For liquid phase reactions, the expression is:
Fi Mi
v =  ------------
ρi
- (2-80)
i

• and for gas phase reactions:

64 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

 Rg T
v = -----------
p  Fi . (2-81)
i

The default value for p (Reactor pressure) is 1 atm in Equation 2-81 and it is set in
the Mixture section.

Reactor Volume
The section sets the Reactor volume Vr , i.e. the fluid volume in which chemical reaction
takes place. The Batch reactor type can account for a changing volume, thus a
time-dependent volume expression can be entered here.

Reactor Types in the Reaction Engineering Interface

CHEMKIN IMPORT FOR SPECIES PROPERTY

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

Two types of CHEMKIN input files can be imported here—Thermo or Transport for
either volumetric or surface species. Click Browse to locate the CHEMKIN file to be
imported, then click Import. The imported data directly enters the NASA format fields
in the Species Thermodynamic Expressions section or the Species Transport Expressions.
section.

• CHEMKIN Data and NASA Polynomials

• Reversible Reaction Group

THE REACTION ENGINEERING INTERFACE | 65

 Features Nodes Available for the Reaction Engineering Interface
The following feature nodes are available from the Reaction Engineering ribbon toolbar
(Windows users), Reaction Engineering context menu (Mac or Linux users), or
right-click to access the context menu (all users).

• Initial Values • Reaction Thermodynamics1

• Reaction • Species Activity1
• Species • Species Thermodynamics1
• Reversible Reaction Group • Feed Inlet
• Equilibrium Reaction Group • Generate Space-Dependent Model
• Species Group • Parameter Estimation2
• Additional Source • Experiment2
1
This is a subnode and it is only available together with a parent node.
2 Requires the addition of the Optimization Module.

Initial Values
The Initial Values node sets the initial values of the dependent variables solved for in
the Reaction Engineering interface.

GENERAL PARAMETERS
For CSTR, constant mass and Semi reactor types, in which the reactor volume changes
with reaction, an Initial system volume Vr0 can be set.

For nonisothermal conditions, i.e. the Energy Balance is set to Include, enter an Initial
temperature T0 for the system. For the Plug flow reactor a corresponding Inlet
temperature T0,in is entered.

VOLUMETRIC SPECIES INITIAL VALUE

In the Volumetric species initial concentration table, the Species column automatically
includes all the species in the model. Enter the corresponding values or expression for
each species initially in the Concentration (mol/m^3) column.

For the Plug flow reactor an Inlet molar flow rate table is instead shown. Enter the values
or expressions representing the inlet conditions of each species in the Molar flow rate
(mol/s) column.

66 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

SURFACE SPECIES INITIAL VALUE
The Surface Species Initial Value table is displayed when surface species are present in
the reactor, i.e. when the Species Type is set to Surface species for at least one species
in the reactor. Enter in the Surface concentration (mol/m^2) column, the corresponding
values or expression for each species initially on the reactive surface area (Ar) within
the reactor. The values in the Site occupancy number column are by default set to 1, edit
the value if a surface species takes up more than one active site on the reactive surface.

The total surface concentration initially is always restricted by the molar amount of
available sites on the reactive surface area. This is defined by the Initial density of surface
sites γ0 (SI unit: mol/m2) entry. Make sure that the sum of the entered initial surface
concentrations do not surpass the value selected here. Note that the actual surface
concentration of each species is the Surface concentration (mol/m^2) multiplied with the
Site occupancy number. The restriction of the total surface concentration is defined as:

γ0 ≥  csurf, i ⋅ numbersite occupancy, i (2-82)

i

REACTOR AREA
This section is displayed when surface species are present in the model. Set the Reactor
area, in other words the total reactive surface area available in the reactor, here.

Reaction
To add a Reaction node ( ) either right-click the Reaction Engineering node or on the
Reaction Engineering toolbar click Reaction.

REACTION FORMULA

Formula
Enter a chemical reaction Formula. Click Apply to make the interface examine the
species taking part in the model’s reactions and automatically add the associated
Species features to the Model Builder.

Reaction Type
Select the Reaction type—Reversible, Irreversible, or Equilibrium—or edit the expression
directly in the Formula field. In the latter case, specify the reaction type with a delimiter
separating the two sides of the equation:

• <=> denotes a Reversible reaction

THE REACTION ENGINEERING INTERFACE | 67

 • => denotes an Irreversible reaction
• = denotes a reaction at chemical Equilibrium

Each Reaction type has its own set of reaction kinetics:

• If the reaction is Reversible or Irreversible, the reaction rate for a species becomes:

dc i
-------- = ν i r (2-83)
dt

• If it is an Equilibrium reaction, the equilibrium expression is equal to the equilibrium

constant:
K eq = K eq0 (2-84)

REACTION RATE
This section is available when the Reaction type is either Reversible or Irreversible.

The Automatic Reaction rate expression is set up according to the mass action law:

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

f – ν ij
rj = kj ∏ ci (2-85)
i ∈ react

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

Qp
f – ν ij r νij
rj = kj ∏ ci – kj ∏ ci (2-86)
i ∈ react i ∈ prod

RATE CONSTANTS
This section applies for Reversible or Irreversible reactions and defines the reaction rate
constants used in the reaction rates.

Forward Rate Constant and Reverse Rate Constant

The Forward rate constant kf is used for both Reversible and Irreversible reactions. The
Reverse rate constant kr is only used for Reversible reactions (Equation 2-86).

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.

68 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

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 (2-87)

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 ) ) (2-88)

f rf
r r n r
k = A ( T ⁄ T ref ) exp ( – E ⁄ ( R g T ) ) (2-89)

Specify the activation energy and the frequency factor in the Arrhenius expressions to
account for temperature variations. The reference temperature, Tref equals 1 K. The
available fields are based on the Reaction type chosen in the Reaction node. Enter
values or expressions for each of the following (reverse expressions are only available
for reversible reactions):

• Forward frequency factor Af and Reverse frequency factor Ar (SI unit: (mβ/
mol)α − 1/s, where α equals the order of the reaction and β is 3 or 2 for volumetric
or surface reactions, respectively)
• Forward temperature exponent 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:

THE REACTION ENGINEERING INTERFACE | 69

 νij
∏ ci
i ∈ prod
K eqj = ---------------------------- (2-90)
– ν ij
∏ ci
i ∈ react

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

Equilibrium Constant
Specify the Equilibrium constant Keq0 for an equilibrium reaction, or for a reversible
reaction when the Specify equilibrium constant check box has been selected (in the Rate
Constants section).

The Equilibrium constant can either be User defined, or automatically defined when set
to Automatic or Thermodynamics.

Use the Automatic option to compute the equilibrium constant for an ideal system.
This setting requires that the temperature is also solved for by setting Energy Balance
to Included.

The Thermodynamics option is available when all reactions in the interface are
equilibrium reactions, and the interface is fully coupled to a Thermodynamic System
(see Species Matching). Use this setting to automatically compute the equilibrium
constant for an ideal or non-ideal system, dependent on the thermodynamic model
applied for the coupled system.

Using Automatic or Thermodynamics, Keq0 is calculated from the Gibbs free energy of
the reaction. For more details see The Equilibrium Constant and the Automatically
Defined Equilibrium Constants section therein.

REACTION THERMODYNAMIC PROPERTIES

This section contains information about thermodynamic properties that relate to a
selected reaction and is available when the Energy Balance is set to Include. 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:

70 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

 Qp Qr

Hj =  νij hi –  ( –νij )hi (2-91)

i=1 i=1

Entropy of Reaction
The Entropy of reaction S (SI unit: J/(mol·K)) comes from a similar expression:

Qp Qr

Sj =  ν ij s i –  ( –νij )si (2-92)

i=1 i=1

In Equation 2-91 and Equation 2-92, hi and si are the species’ molar enthalpy and
molar entropy, respectively.

Enter these quantities in the Species Thermodynamic Expressions section for the Species
node either by using the predefined polynomial or by providing a custom expression
or constants.

The stoichiometric coefficients, vij, are defined as being negative for reactants and
positive for products. Using Equation 2-91 and Equation 2-92 to equate the Gibbs
free energy of reaction enables the equilibrium constant to be expressed according to
Handling of Equilibrium Reactions.

Heat Source of Reaction

The Heat source of reaction (SI unit: W/m3) is automatically computed from the heat
of each reaction j, given by:

Qj = –Hj rj

Using the Reaction Node

Species
When a Reaction is defined, a Species node ( ) is automatically generated for the
participating reactants and products. This feature enables you to review and enter
species specific information regarding chemical kinetics, thermodynamics and
transport properties.

THE REACTION ENGINEERING INTERFACE | 71

 It is also possible to add and define an individual Species node: on the Reaction
Engineering toolbar click Species or right-click the Reaction Engineering node and select
it from the context menu.

SPECIES NAME
When a Species node is automatically generated using the Formula text field for the
Reaction node, the Species name is also automatically generated.

For a Species node added individually, enter a Species name in the field and click Apply.

Creating Valid Species Names and Labeling

SPECIES TYPE
Select a Species type—Bulk species, Surface species, or Solvent.

Bulk species and Solvent are solved for volumetric concentrations (SI unit: mol/m3),
while Surface species are solved for surface concentration (SI unit: mol/m2). The
compositions for Bulk species and Solvent use the syntax c_speciesname, while Surface
species uses csurf_speciesname_surf.

Surface species is referring to species adsorbed on a reactive surface. 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.

For the Plug flow reactor only Bulk species and Solvent are allowed.

Choosing the Species Type

GENERAL PARAMETERS
The General Parameters section deals with species parameters.

Edit, if necessary, the species Molar mass M and the ionic Charge z of the species in
question.

It is possible to specify the species density ρ when the fluid Mixture is specified as Liquid.
The default value is that of water at 293 K.

72 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

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 (i.e. non-reactive).

Edit either the Rate expression (SI unit: mol/(m3s)), the Surface rate expression (SI
unit: mol/(m2s)), or both. For a bulk species, both expressions appear if surface
reactions are present in the reactor since the reaction of the species can depend both
on bulk reaction R and surface reaction Rads rates. For a surface species, only the
surface reaction rate Rads appears.

The reaction rate is not editable if the species in question participates in an equilibrium
reaction and has been selected as a Predefined dependent species in Equilibrium Species
Vector.

SPECIES CONCENTRATION/ACTIVITY
To account for non-ideality in the fluid mixture adjust the activity coefficient in the
Activity coefficient text field here. The section is only shown if activity instead of
concentration has been chosen in the interface, i.e. the Use activities check box is
selected on the Reaction Engineering interface Settings window

Click to select the Locked concentration/activity check box if the species concentration
or activity should be treated as constant.

THE REACTION ENGINEERING INTERFACE | 73

 SPECIES TRANSPORT EXPRESSIONS
Here the required parameters to compute various transport properties can be edited.
To show this section the Calculate mixture properties check box needs to be selected
under the Calculate Transport Properties section.

• For a gas mixture, there are maximum five properties to consider:

- σ, the characteristic length (unit: Å) of the Lennard-Jones/Stockmayer potential
- ε/kb (SI unit: K) the potential energy minimum value of the of the
Lennard-Jones/Stockmayer potential, divided by Boltzmann’s constant.
Tabulated data in literature frequently lists values of ε/kb rather than ε
- μD, the dipole moment (SI unit: Debye)
- ki, the thermal conductivity of the gas (SI unit: W/(m K)); and Diffusivity of the
species (SI unit: m2/s). The latter two can be set to Automatic, when σ and ε/kb
have been given.
• For mixtures of gas with solvent, all properties above except the thermal
conductivity is shown. This is instead calculated under the Calculate mixture
properties section on the Settings window for the Reaction Engineering interface.
This requires that Energy Balance is set to Included.
• For a liquid mixture, there is only the parameter ki, the thermal conductivity (SI
unit: W/(m K)) to edit.
• For mixtures of liquid with solvent, the thermal conductivity is shown only for the
species set as Solvent.

SPECIES THERMODYNAMIC EXPRESSIONS

The parameters utilized for calculation of thermodynamic mixture and reaction
properties are set in this section. It is accessed when the Energy Balance is set to Include
for the Reaction Engineering interface, in other words for nonisothermal conditions.

The Species enthalpy is by default computed with the NASA format. In this case, enter
the following to compute the species’ heat capacity, Cp (SI unit: J/(mol⋅K)), the molar
enthalpy, h (SI unit: J/mol), and the molar entropy, s (SI unit: J/(mol⋅K)):

• Lower temperature limit Tlo

• Middle temperature limit Tmid
• Upper temperature limit Thi
• Polynomial coefficients alow,k and ahi,k

74 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

Any coefficients for the thermodynamic polynomials entered into the alow,k fields
apply to the temperatures in the range Tlo to Tmid; coefficients entered into the ahi,k
fields apply to temperatures in the range Tmid to Thi range. The coefficients can also
be imported in the CHEMKIN Import for Species Property section in the Reaction
Engineering node.

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

Using the Species Node

Transport Properties

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. The feature is typically used
when importing CHEMKIN kinetics files.

Add the node from the Reaction Engineering toolbar or right-click Reaction Engineering
and add it from the context menu.

For the case when reaction kinetics data are entered manually into the Reaction table
and nonisothermal conditions apply (Energy Balance is set to Include), right-click to
add a Reaction Thermodynamics subnode or select it from the Reaction Engineering
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.

THE REACTION ENGINEERING INTERFACE | 75

 • You can save the parameters to a text file to reuse in other models. Click the Save to
File button ( ) and enter a File name in the Save to File dialog box, including the
extension.txt. Click Save to store the parameters in a text file or in a Microsoft Excel
Workbook spreadsheet if the license includes LiveLink™ for Excel®. The information
is saved in space-separated columns in the same order as displayed on screen. When
saving to Excel, an Excel Save dialog box appears where you can specify the sheet and
range and whether to overwrite existing data, include a header, or use a separate
column for units.
• You can import or load data in files from a spreadsheet program, for example, with
the Load from File button ( ) and the Load from File dialog box that appears. Data
must be separated by spaces or tabs. If there is already data in the table, imported
parameters are added after the last row. Move or edit rows as needed. If the license
includes LiveLink™ for Excel® you can also load parameters from a Microsoft Excel
Workbook spreadsheet. Then an Excel Load dialog box appears where you can specify
the sheet and range and whether to overwrite existing data. It is also possible to
import from a spreadsheet containing a separate column for units.

In the case of twenty or more reactions the Disable updating variables during editing
table check box is available. Select this to speed up editing text fields; automatic
updates related to edits do not occur until you click to clear the check box.

CHEMKIN IMPORT FOR KINETICS

Click to select the Import CHEMKIN data check box to import a CHEMKIN Kinetics
input file. To import the data directly into the table columns, click Browse to locate the
CHEMKIN file to be imported, then click Import.

CHEMKIN Data and NASA Polynomials

MOVE REACTION AND SPECIES

Enter a reaction number in the Moving reaction (with the number) from table text field
and click Create Reaction to remove the reaction from the Reaction table to the model
tree. This introduces a reaction node named after the reaction number and species
names and simultaneously creates corresponding species nodes. This action is
powerful, since it enables all the editing possibilities available for Reaction and Species
nodes.

76 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

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 Reaction Engineering toolbar or right-click Reaction Engineering
and add it from the context menu.

For the case when reaction kinetics data are entered manually into the Reaction table
and nonisothermal conditions apply (Energy Balance is set to Include), right-click to
add a Reaction Thermodynamics subnode or select it from the Reaction Engineering
toolbar, Attributes menu. In it, the Enthalpy of Reaction (J/mol) for each reaction can
be specified.

EQUILIBRIUM REACTION TABLE

The equilibrium reactions in the Reaction table are numbered and contain reactants,
products, and kinetic parameters describing the reaction. Use the buttons under the
Reaction table to add and sort the reaction details.

• In general, use the Move Up ( ), Move Down ( ), and Delete ( ) buttons and
the fields under tables to edit the table contents. Or right-click a table cell and select
Move Up, Move Down, or Delete.
• The Add button ( ) adds default reactant, A, and product, B, with a default. Click
the corresponding field to edit the reactant, product, or parameters. After editing
the Species Group node is also updated. It is created together with the reaction
group.
• You can save the parameters to a text file to reuse in other models. Click the Save to
File button ( ) and enter a File name in the Save to File dialog box, including the
extension.txt. Click Save to store the parameters in a text file or in a Microsoft Excel
Workbook spreadsheet if the license includes LiveLink™ for Excel®. The information
is saved in space-separated columns in the same order as displayed on screen. When
saving to Excel, an Excel Save dialog box appears where you can specify the sheet and
range and whether to overwrite existing data, include a header, or use a separate
column for units.
• You can import or load data in files from a spreadsheet program, for example, with
the Load from File button ( ) and the Load from File dialog box that appears. Data
must be separated by spaces or tabs. If there is already data in the table, imported
parameters are added after the last row. Move or edit rows as needed. If the license
includes LiveLink™ for Excel® you can also load parameters from a Microsoft Excel

THE REACTION ENGINEERING INTERFACE | 77

 Workbook spreadsheet. Then an Excel Load dialog box appears where you can specify
the sheet and range and whether to overwrite existing data. It is also possible to
import from a spreadsheet containing a separate column for units.

In the case of twenty or more reactions the Disable updating variables during editing
table check box is available. Select this to speed up editing text fields; automatic
updates related to edits do not occur until you click to clear the check box.

MOVE REACTION AND SPECIES

Enter a reaction number in the Moving reaction (with the number) from table text field
and click Create Reaction to remove the reaction from the Reaction table to the model
tree. This introduces a reaction node named after the reaction number and species
names and simultaneously creates corresponding species nodes. This action is
powerful, since it enables all the editing possibilities available for Reaction and Species
nodes.

Homogeneous Charge Compression Ignition of Methane: Application

Library path Chemical_Reaction_Engineering_Module/Ideal_Tank_Reactors/
compression_ignition

Chemical Vapor Deposition of GaAs: Application Library path

Chemical_Reaction_Engineering_Module/
Reactors_with_Mass_and_Heat_Transfer/gaas_cvd

Species Group
The Species Group node ( ) contains information on a molecular level about the
volumetric species and the surface species present in the model. The Property for
Volumetric Species or Property for Surface Species tables typically collect parameters
from when importing CHEMKIN transport files.

Add the node from the Reaction Engineering toolbar or right-click Reaction Engineering
and add it from the context menu. This node is also automatically added when either
the Reversible Reaction Group or the Equilibrium Reaction Group are used.

For the case of nonisothermal reactor conditions (Energy Balance is set to Include), a
Species Thermodynamics subnode is automatically created in which the
thermodynamic properties of the species can be specified.

78 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

CHEMKIN
This section allows import of CHEMKIN transport files. To import the data directly
into the table columns, click Browse to locate the CHEMKIN file to be imported, then
click Import. Note that this section is only shown when transport properties are
computed (Calculate mixture properties check box under the Calculate Transport
Properties is selected).

CHEMKIN Data and NASA Polynomials

Additional Source
Use the Additional Source node ( ) to add an additional rate expression (SI unit:
mol/m ) and/or an additional volumetric production rate (SI unit: m3/s) to the mass
3

balance of certain species.

Add the node from the Reaction Engineering toolbar or right-click Reaction Engineering
and add it from the context menu.

ADDITIONAL VOLUMETRIC PRODUCTION RATE

An additional Additional volumetric production rate can be added for some of the
available reactor types, namely CSTR, constant mass/generic, CSTR, constant volume, or
Semi.

ADDITIONAL RATE EXPRESSION

Here, values or expressions describing additional rates can be entered for selected
Species in the column denoted Additional rate expression (mol/m^3*s) within the
Volumetric species table.

ADDITIONAL SURFACE SPECIES RATE

Here, values or expressions describing additional surface species rates can be entered
for selected Surface species in the column denoted Additional rate expression (mol/
m^3*s) within the Surface species table.

THE REACTION ENGINEERING INTERFACE | 79

 Reaction Thermodynamics
In 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 Reaction Engineering toolbar,
Attributes menu. Alternatively, when the Energy Balance is set to Include, right-click a
Reversible Reaction Group or Equilibrium Reaction Group and select it from the
context menu.

Species Activity
The Species Activity node ( ) creates variables for the activities for all the species/
surface species present in the Species Group parent feature. Edit the Activity coefficient
field in the Species Activity or Surface Species Activity tables by clicking in these.

Species Activity is a subnode to the Species Group node. It is automatically generated

when non-ideality in the fluid mixture is accounted for; when the Use activity check
box is selected in the Activity section.

Species Thermodynamics
The Species Thermodynamics node ( ) creates variables for the enthalpies, entropies,
and heat capacities for all the species/surface species present in the Species Group
parent feature. The purpose is to compute thermodynamic mixture properties and the
heat of reactions.

This node is a subnode to the Species Group node when the Energy Balance is set to
Include.

SPECIES THERMODYNAMICS PROPERTY

Select a Type selection for the thermodynamic properties. The NASA format alternative
requires the setting of several polynomial constants and is typically used together with
CHEMKIN import. The User defined alternative only requires input of Species molar
enthalpy (J/mol) and Species molar capacity (J/(mol*K)).

CHEMKIN IMPORT FOR THERMODYNAMIC DATA

This section allows import of thermodynamic CHEMKIN transport files. To import
the data directly into the table columns, click Browse to locate the CHEMKIN file to

80 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

be imported, then click Import. Note that this can only be done for the NASA format
option.

• CHEMKIN Data and NASA Polynomials

Feed Inlet
The Feed Inlet ( ) feature is used for adding inlet streams to the reactor.

After adding a Reaction node and setting its Reactor Type to CSTR, constant volume,
CSTR, constant mass/generic, or Semi, add a Feed Inlet node from the Reaction Engineering
toolbar or right-click the Reaction Engineering node to add it from the context menu.

FEED INLET PROPERTIES

Edit the Volumetric feed rate (vf) (SI unit: m3/s) to fit the modeling conditions.

The Feed inlet temperature (Tf) is required as input when nonisothermal conditions are
investigated (Energy Balance is set to Include).

FEED STREAM CONCENTRATION

For each of the Species, enter a value or expression in the table for the Concentration
(mol/m^3) to set the composition of the inlet stream.

FEED STREAM CONCENTRATION AND ENTHALPY

For each of the Species, enter values or expressions in the table for the Concentration
(mol/m^3) and Enthalpy (J/mol) to set both the composition and enthalpy of the feed
inlet stream. Note that in the rightmost column of the Feed inlet concentration and
enthalpy table, it is possible to select that the thermodynamic properties are taken from
a Species node instead.

• CSTR, Constant Mass/Generic

• CSTR, Constant Volume
• Semibatch

THE REACTION ENGINEERING INTERFACE | 81

 Generate Space-Dependent Model
It is often relevant to perform an extended analysis of the reaction model. For example,
to study how a reacting system’s detailed geometry impacts the concentration and
temperature distributions. Use the Generate Space-Dependent Model feature tool to
export the properties within the Reaction Engineering interface to other COMSOL
Multiphysics interfaces where a space-dependent model is set up. Properties that are
exported are reaction kinetics, thermodynamics, and transport parameters.

To add this feature, on the Reaction Engineering toolbar click Generate Space-Dependent
Model ( ) or right-click the Reaction Engineering node to add it from the context
menu. Only one Generate Space-Dependent Model node can be added per model file.

SELECTING THE MODEL GENERATION SETTINGS

To utilize the Generate Space-Dependent Model feature make selections in the following
order:

1 Select the component to use: 1D axi, 1D, 2D, 2D axi, 3D, or an existing component
within the model builder.
2 Select the physics interfaces.
3 Select a study type.

82 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

Then click the Create/refresh button to create the space-dependent model
(Figure 2-5).

Figure 2-5: The Generate Space-Dependent Model transfers the properties from the
Reaction Engineering interface to physics interfaces in a1D axi, 1D, 2D, 2D axi, or 3D
component.

If more interfaces are needed in a component after the initial model generation, select
the component and the new interface(s) and click Create/refresh to introduce the
interface into it.

COMPONENT SETTINGS
Select a Component to use. Either specify the space dimension of a new component—
1D, 1Daxi, 2D, 2Daxi, and 3D—or select a component already defined in the Model
Builder.

THE REACTION ENGINEERING INTERFACE | 83

 PHYSICS INTERFACES
Select the applicable physics interfaces to create or update from the Chemical species
transport, Fluid flow, and Heat transfer lists. The physics interfaces available are based
on the specific modules installed. These include the Chemical Reaction Engineering
Module, the MEMS Module, the Heat Transfer Module, and the Subsurface Flow
Module. Note that a mass balance physics interface must always be selected when
generating a space-dependent model.

If desired, physics interfaces for fluid flow, heat transfer, or other features affecting the
reacting system can be added later separately from the physics interfaces created by the
Generate Space-Dependent Model feature.

The Chemistry Interface is always created and added when generating a

space-dependent model. It generates and announces global variables for the reaction
kinetics, thermodynamics, and transport properties from the Reaction Engineering
interface. The global variables generated are available for all space-dependent
interfaces. Figure 2-6 displays an application where a Reactions feature uses reaction
rates defined by a Chemistry interface. The syntax chem points to the default Name of
the Chemistry node.

84 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

Figure 2-6: The Chemistry node generates global variables from rate variables and
properties defined in the Reaction Engineering interfaces, and announces these to be used
in relevant sections of other generated space-dependent interfaces. The Reaction Rates
within a Reactions feature in a Transport of Dilute Species interface illustrate this.

If necessary, variables and properties in the Chemistry node can be accessed with the
Chemistry node Name (default Chem). An arbitrary reaction rate expression, R, is thus

THE REACTION ENGINEERING INTERFACE | 85

 written as comp2.chem.R in the corresponding text fields of the generated interface
(see Figure 2-6).

When surface species are present (that is, when the Species Type is set to Surface species
for at least one species in the reactor), specify how to include surface reactions in the
space-dependent model.

From the Surface reaction on list, select Boundaries or Porous Pellets.

• When Boundaries is selected, the surface reactions will be modeled using a Surface
Reactions interface defined on the boundaries of the geometry.
• When Porous Pellets is selected, the surface reactions will be modeled using a
Reactive Pellet Bed feature added to a Transport of Diluted Species interface or a
Diluted Species in Porous Media interface. In this case the content of the Mass balance
list is restricted to these interfaces.

A corresponding reaction feature is added and set up, in accordance with the reaction
kinetics defined in the Reaction Engineering interface, when clicking the Create/Refresh
button in the Space-Dependent Model Generation section. In Figure 2-7, the surface
reaction kinetics in a Reacting Engineering interface has been implemented in a Reactive
Pellet Bed feature using a Reactions subfeature. Note that the surface reaction rates are
defined by the Chemistry interface.

86 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

Figure 2-7: A Reactive Pellet Bed feature with a Reactions subfeature can be
automatically created, using a Generate Space-Dependent Model feature, from a
Reaction Engineering interface containing surface species.

• Theory for the Reactive Pellet Bed

• The Transport of Diluted Species Interface

Chemical Species Transport

The following Chemical Species Transport interfaces are available with the Chemical
Reaction Engineering Module:

• The Transport of Diluted Species Interface

• The Transport of Diluted Species in Porous Media Interface
• The Nernst-Planck Equations Interface
• The Transport of Concentrated Species Interface

THE REACTION ENGINEERING INTERFACE | 87

 The model generation automatically defines the dependent variables for all species.
The Transport of Diluted Species, Nernst-Planck Equations, and Transport of Diluted
Species in Porous Media interfaces use the default variable names according to the
syntax cspeciesname, referring to species concentrations in mole per volume. The
Transport of Concentrated Species interface uses the syntax wspeciesname for default
variable names, referring to the species weight fraction. The initial values for the
dependent species variables in the space-dependent model, are based on the initial
species values collected in the Reaction Engineering interface. Note that only the
Transport of Diluted interface is available for systems with equilibrium reactions.

Binary diffusion coefficients of different kinds can be computed and transferred to a

space-dependent model. The available diffusion models for the mass balance physics
interfaces sometimes require the binary diffusion coefficients of the mixture,
describing all pairwise diffusion interactions between species. Under the assumption of
an ideal gas the Transport of Concentrated Species interface can utilize the binary
diffusion coefficient. The Transport of Diluted Species and Nernst-Planck Equations
interfaces assumes that the chemical species being transported are present in small
amounts and are diluted in a solvent. The binary diffusion coefficient in these cases (in
the presence of a solvent species) become the diffusion coefficient of the bulk species.

Heat Transfer
The Reaction Engineering interface can also be set up with time- and space-dependent
energy balance equations. In the model generation process the physics interface
generates expressions used by the Heat Transfer interface, such as the heat generated
by a chemical reaction. It also generates expressions for physical transport properties.

There are two heat transfer interfaces under the Energy balance:

• Heat Transfer in Fluids

• Heat Transfer in Porous Media

Several expressions for the species density, heat capacity, and thermal conductivity are
available and can be transferred from the Reaction Engineering interface.

The densities are available from the Mixture section in the interface, where the fluid
mixture properties are selected. The density depends on the Species settings and is
computed as follows for:

• Liquid, if assuming the liquid to be ideal and incompressible. The liquid mixture
density depends on the density of i number of pure species, ρi, and the species
weight fraction, wi.

88 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

 1
ρ = -------------- (2-93)
wi

------
ρi
i

The volume fraction is given by the species concentration, ci, and the molar mass,
Mi.
ci Mi
w i = -------------------- (2-94)
 ci Mi
i

• Gas mixture density depends on the concentrations and molar masses of the mixture
species.

ρ =  ci Mi (2-95)
i

For mixtures with solvent all values are taken from the species set as solvent.
The heat capacity, cp (SI unit: J/(mol·kg)), of the mixture is calculated by the
species’ molar heat capacity, Cp (SI unit: J/(mol·kg)) according to
C p, i
cp =  wi ----------
Mi
- (2-96)
i

where M is the molar mass (SI unit: kg/mol) and wi the weight fraction.

Fluid Flow
The model generation process can be selected to generate a Fluid Flow interface.

There are these separate momentum balance physics interfaces:

• The Single-Phase Flow, Laminar Flow Interface

• The Darcy’s Law Interface (in the CFD Module User’s Guide)
• The Free and Porous Media Flow Interface (in the CFD Module User’s Guide)

Species density (see Equation 2-93, Equation 2-94, and Equation 2-95) and dynamic
viscosity can for some mixture options be transferred from the Reaction Engineering
interface to the Fluid Flow interfaces.

Transport Properties

THE REACTION ENGINEERING INTERFACE | 89

 NOx Reduction in a Monolithic Reactor: Application Library path
Chemical_Reaction_Engineering_Module/Tutorials/monolith_3d

Hydrocarbon Dehalogenation in a Tortuous Microreactor: Application

Library path Chemical_Reaction_Engineering_Module/
Reactors_with_Mass_Transfer/tortuous_reactor

Protein Adsorption: Application Library path

Chemical_Reaction_Engineering_Module/Mixing_and_Separation/
protein_adsorption

STUDY TYPE
Select a Study Type, either Stationary or Time Dependent. It is also possible to edit this
choice after the space-dependent model has been generated.

Parameter Estimation
The Parameter Estimation feature ( ) requires the Optimization Module.

Add the node from the Reaction Engineering toolbar or right-click Reaction Engineering
and add it from the context menu. The node and related subnodes have the options
and settings for the definition of parameter estimation calculations based on the
predefined reactor types in the Reaction Engineering interface.

ESTIMATION PARAMETERS
The parameters to be estimated are defined in the Estimation parameters table. The
parameter names are entered in the Parameter column. An Initial value is also required
for each variable. To connect the estimated parameters to the model, make sure that
the same parameter naming is used within the rest of the Reaction Engineering
interface.

Bounds for the parameter values are specified in the Lower bound and Upper bound
columns of the Estimation parameters table. These are applicable when the SNOPT
optimization (Solver Study Steps for Parameter Estimation) solver method is used. The
default solver method for parameter estimation is Levenberg-Marquardt, which
currently does not support parameter bounds. Enter a Scale indicating a typical
magnitude of the control variable. The relative solver tolerances refer to variables
rescaled with respect to this scale, and it may also influence the search pattern of some
optimization solvers.

90 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

Experiment
The Experiment node organizes the data and the conditions for a particular experiment.
This is also where experimental variables are associated with model variables in order
to set up the parameter estimation.

Right-click the Parameter Estimation node to add one or more Experiment nodes. You
can also select it from the Reaction Engineering toolbar, Attributes menu. The
Experiment node requires the Optimization Module.

EXPERIMENTAL DATA
Experimental data is read into the software by importing comma-separated value files,
CSV files. After import, identifiers display in the Data column of the Experimental Data
table (Figure 2-8). If the CSV files have column headers, these are used to identify the
columns. If the data file does not have column headers, the columns are identified by
a number. It is assumed that the first column corresponds to the independent variable
for time (t). In the Model variables column, the measured data is correlated with model
variables by entering the proper variable names or expressions. The Use column
controls whether to include data in the parameter estimation calculation or not. Data
column entries require associated Model variables to be accounted for the parameter
estimation calculations.

In the Unit column, enter the unit of the imported experimental data.

In the Weight column, enter a strictly positive value. The difference between the value
of the Model variable and the Data column value is squared and multiplied with the
Weight and a factor 0.5 to give the contribution to the total objective for each
measured value.

THE REACTION ENGINEERING INTERFACE | 91

 Imported data can be inspected in the corresponding Table node located under the
Results branch (Figure 2-8). An Experiment Table is created each time the Import
button is clicked.

Figure 2-8: The content of imported data files is presented in a Table.

EXPERIMENTAL PARAMETERS
Each Experiment node can be associated with user-defined parameters during the
parameter estimation. For example, concentration transients can be measured for a
number of different isothermal conditions. Parameter name and Parameter expression
are added from a list. The list is populated with the parameters that are defined in the
Parameters under Global Definitions in the Model Builder.

INITIAL STATES
A given experiment usually determines the initial values for the dependent variables in
the reactor model, such as the initial concentrations for isothermal reactor models and
initial concentrations and temperature for non-isothermal reactor models.

Initial conditions that change from one experiment to another need to be provided in
the Initial States section of the Experiment node. An entry in the Parameter names
column is added by choosing from a list of predefined variable names corresponding
to the initial state of the reactor model.

92 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

Degradation of DNA in Plasma: Chemical_Reaction_Engineering_Module/
Ideal_Tank_Reactors/dna_degradation

Finding Kinetic Arrhenius Parameters Using Parameter Estimation:

Chemical_Reaction_Engineering_Module/Tutorials/activation_energy

• Solver Study Steps for Parameter Estimation

• www.comsol.com/optimization-module

THE REACTION ENGINEERING INTERFACE | 93

 The Chemistry Interface
This physics interface can be used to create reaction kinetics and optionally compute
transport and thermodynamic properties for direct use in 1D, 2D, or 3D models. This
is similar to The Reaction Engineering Interface, except that it does not solve for an
ideal reactor model.

The Chemistry (chem) interface ( ) is found under the Chemical Species Transport
branch ( ) when adding a physics interface. The Chemistry interface is also created
when the Generate Space-Dependent Model feature is used in the Reaction
Engineering interface, collecting all mixture variables and properties for use in a
space-dependent model.

This physics interface is a tool for generating a set of variables to be used for modeling
chemical species and reactions systems. The variables are generated from species and
reaction properties and can be divided in two categories:

• Rate expressions and heat sources for use in mass and heat balances
• Material property variables (mixture density, diffusivities, viscosity, etc.) for use in
space-dependent transport equations.
Many of the fields and nodes described in this section are only made available when
either a Reaction or a Species (or both) subnode is added to the Model Builder. All
predefined constants and expressions can be overwritten by user-defined expressions.
This makes it possible to go beyond the modeling assumptions set as defaults in this
physics interface.

• Theory for the Reaction Engineering and Chemistry Interfaces

• Transport Properties
• Feature Nodes Available for the Chemistry 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

94 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

<name>.<variable_name>. In order to distinguish between variables belonging to
different physics interfaces, the name string must be unique. Only letters, numbers and
underscores (_) are permitted in the Name field. The first character must be a letter.

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

MODEL INPUTS
This section sets the Temperature and Pressure. In the lists, it is possible to edit the User
defined option to the temperature and pressure from interfaces available in the Model
Builder. The latter choice couples the interfaces.

SPECIES MATCHING
Use the table in this section to specify the concentrations for the variables generated
by the Reaction and the Species features (the reaction rate for example), and to define
mixture properties (transport and thermodynamic properties).

Select Diluted Species in the Mixture type list to use the concentration variables from a
Transport of Diluted Species interface. The same setting should be used for any other
interface solving for species concentrations using a diluted species assumption. Enter
the names of the dependent variables in the Molar concentration column.

Select Concentrated Species in the Mixture type list in order to use the mass fractions
from a Transport of Concentrated Species interface. Enter the names of the dependent
variables in the Mass fraction column.

The name of the reaction rate variables generated by the interface can be seen in the
Reaction Rate column of the table. The syntax of the reaction rate variables depend on
the Species type selected in the Species Settings window. Bulk species and Solvent use
the syntax R_speciesname, while Surface species uses R_speciesname_surf.
Selecting Concentrated species for the Mixture type, the base of syntax for the reaction
rate is changed. to Rw_speciesname.

EXTRA DIMENSION
Select Define variables in extra dimension when the current Chemistry interface is
coupled to a feature on an extra dimension. An example of this is when the
concentrations in the Concentration input column of the Model Inputs, Concentration
corresponds to pellet concentrations from a Reactive Pellet Bed feature in a Transport
of Diluted Species interface.

When selected, generated variables will be defined using concentrations averaged over
the extra dimension. Note that the generated variables are global in order be available

THE CHEMISTRY INTERFACE | 95

 on the main geometry, in contrast to variables on the extra dimension which only exist
on the corresponding dimension.

MIXTURE
Select a Mixture to specify the phase, Gas or Liquid, of the reaction fluid.

Mixture Density
Mixture density always has two settings available: Automatic or User defined. The density
is compiled for both multicomponent and solute-solvent solutions.

• Automatic (ideal liquid) selected for Liquid, considers the liquid as ideal and
incompressible. The liquid mixture density depends on the density of i number of
pure species (ρi) and the species weight fraction (wi).
1
ρ = --------------
wi
 ------
ρi
i

The volume fraction is given by the species concentration (ci) and the molar mass
(Mi).
ci Mi
w i = --------------------
 ci Mi
i

• Automatic set for Gas calculates the gas mixture density (ρ) from the concentrations
(ci) and molar masses (Mi) of the mixture species, which are automatically taken
from Species features.

ρ =  ci Mi (2-97)
i

• If a Species Type is set to Solvent and the Mixture is Liquid, the mixture density is the
same as the solvent density as defined in Density in General parameters in the Species
node. When Mixture is Gas, the mixture density is calculated from Equation 2-97
only for the species set as Solvent.

ACTIVITY
Select the Use activity check box to solve for species activities instead of species
concentrations, which is a common approach when non-ideal fluids are modeled.

96 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

An activity coefficient other than 1 can be set for each species for the Species node in
the Species Concentration/Activity section.

Activity

CALCULATE THERMODYNAMIC PROPERTIES

Select the Calculate thermodynamic properties check box to enable the interface to
compute thermodynamic properties, especially critical if the reaction kinetics are
defined at nonisothermal conditions. The setting here also controls whether
thermodynamic mixture properties becomes available in Calculate Transport
Properties section.

CALCULATE TRANSPORT PROPERTIES

Select the Calculate mixture properties check box to calculate mixture properties that
can be picked up in the space-dependent model interfaces. The properties that can be
calculated are shown beneath the check box. Consider also if the in-built Automatic
expressions fits the model or if User defined expressions are more suitable. In general,
the Chemistry interface calculates properties in the same way as the Reaction
Engineering interface.

Transport Properties

Feature Nodes Available for the Chemistry Interface

The following feature nodes are available from the Chemistry ribbon toolbar (Windows
users), Chemistry context menu (Mac or Linux users), or right-click to access the
context menu (all users).

• Equilibrium Reaction Group • Species

• Reaction • Species Activity
1
• Reaction Thermodynamics • Species Group
• Reversible Reaction Group • Species Thermodynamics1
1 This is a subnode and it is only available together with a parent node.

THE CHEMISTRY INTERFACE | 97

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

REACTION FORMULA

Formula
Enter a chemical reaction Formula. Click Apply to make the interface examine the
species taking part in the model’s reactions and automatically add the associated
Species features to the Model Builder.

Reaction Type
Select the Reaction type — Reversible, Irreversible, or Equilibrium — or edit the
expression directly in the Formula field. In the latter case, specify the reaction type with
a delimiter separating the two sides of the equation:

• <=> denotes a Reversible reaction

• => denotes an Irreversible reaction
• = denotes a reaction at chemical Equilibrium

Each Reaction type has its own set of reaction kinetics:

• If the reaction is Reversible or Irreversible, the reaction rate for a species is:
Ri = νi r (2-98)

• If the reaction is at Equilibrium, the equilibrium expression is equal to the

equilibrium constant:
K eq = K eq0

REACTION RATE
This section is available when the Reaction type is either Reversible or Irreversible.

The Automatic Reaction rate expression is set up according to the mass action law:

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

f – ν ij
rj = kj ∏ ci
i ∈ react

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

98 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

 f – ν ij νij
∏
r
rj = kj ci – kj ∏ ci (2-99)
i ∈ react i ∈ prod

RATE CONSTANTS
This section applies for Reversible or Irreversible reactions and defines the reaction rate
constants used in the reaction rates.

Forward Rate Constant and Reverse Rate Constant

The Forward rate constant kf is used for both Reversible and Irreversible reactions. The
Reverse rate constant kr is only used for Reversible reactions (Equation 2-99).

The SI units of the rate constants are automatically based on the order of the reaction
with respect to the concentrations, as defined in the Reaction formula.

Specify Equilibrium Constant

The Specify equilibrium constant check box is available for Reversible reactions. If the
check box is selected the rate constants are defined in a different manner with the
reverse rate constant being computed from the following expression:

r f
k = k ⁄ K eq0

Thus, in this case, the forward rate constant and equilibrium constant for the reaction
are needed. The Equilibrium constant is edited in the Equilibrium Settings section.

Use Arrhenius Expressions

When the Use Arrhenius expressions check box is selected the Arrhenius parameters are
automatically used in predefined expressions for the forward and reverse rate constants
kfand kr, respectively.
f
f f n f
k = A ( T ⁄ T ref ) exp ( – E ⁄ ( R g T ) )

f rf
r r n r
k = A ( T ⁄ T ref ) exp ( – E ⁄ ( R g T ) )

Specify the activation energy and the frequency factor in the Arrhenius expressions to
account for temperature variations. The reference temperature, Tref equals 1 K. The
available fields are based on the Reaction type chosen in the Reaction node. Enter

THE CHEMISTRY INTERFACE | 99

 values or expressions for each of the following (reverse expressions are only available
for reversible reactions):

• Forward frequency factor Af and Reverse frequency factor Ar (SI unit: (mβ/
mol)α − 1/s, where α equals the order of the reaction and β is 3 or 2 for volumetric
or surface reactions, respectively)
• Forward temperature exponent nf and Reverse temperature exponent nr
• Forward activation energy Ef and Reverse activation energy Er (SI unit: J/mol)

EQUILIBRIUM SETTINGS
This section is available for equilibrium reactions, and for reversible reactions when the
Specify equilibrium constant check box has been selected.

Equilibrium Expression
For an equilibrium reaction, specify the Equilibrium expression. When the Equilibrium
expression is set to Automatic the following expression is used:

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

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

Equilibrium Constant
Specify the Equilibrium constant Keq0 for an equilibrium reaction, or for a reversible
reaction when the Specify equilibrium constant check box has been selected (in the Rate
Constants section).

The Equilibrium constant can either be User defined, or automatically defined when set
to Automatic or Thermodynamics.

Use the Automatic option to compute the equilibrium constant for an ideal system.
This settings requires that the Calculate thermodynamic properties in the corresponding
section is selected.

The Thermodynamics option is available when all reactions in the interface are
equilibrium reactions, and the interface is fully coupled to a Thermodynamic System
(see Species Matching). Use this setting to automatically compute the equilibrium

100 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

constant for an ideal or non-ideal system, dependent on the thermodynamic model
applied for the coupled system.

Using Automatic or Thermodynamics, Keq0 is calculated from the Gibbs free energy of
the reaction. For more details see The Equilibrium Constant and the Automatically
Defined Equilibrium Constants section therein.

REACTION THERMODYNAMIC PROPERTIES

This section has information about thermodynamic properties that relate to a selected
reaction and is available when the Calculate Thermodynamic Properties check box is
selected for the Chemistry interface. Several Automatic definitions are available here.

Enthalpy of Reaction
The Enthalpy of reaction H (SI unit: J/mol) is calculated by the interface from species
properties and the related stoichiometric coefficients:

Hj =  ν ij h i –  ( – ν ij )h i (2-100)
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 (2-101)
i ∈ prod i ∈ react

In Equation 2-100 and Equation 2-101, hi and si are the species’ molar enthalpy and
molar entropy, respectively.

Enter these quantities in the Species Thermodynamic Expressions section for the Species
node either by using the predefined polynomial or by providing a custom expression
or constants.

The stoichiometric coefficients, vij, are defined as being negative for reactants and
positive for products. Using Equation 2-100 and Equation 2-101 to equate the Gibbs
free energy of reaction enables the equilibrium constant to be expressed according to
Equation 2-100.

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:

THE CHEMISTRY INTERFACE | 101

 Qj = –Hj rj

Using the Reaction Node

Species
When a Reaction is defined, a Species node ( ) is automatically generated for the
participating reactants and products. This feature enables you to review and enter
species specific information regarding chemical kinetics, thermodynamics and
transport properties.

It is also possible to add and define an individual Species node: on the Chemistry toolbar
click Species or right-click the Chemistry node and select it from the context menu.

SPECIES NAME
When a Species node is automatically generated using the Formula text field for the
Reaction node, the Species name is also automatically generated.

For a Species node added individually, enter a Species name in the field and click Apply.

Creating Valid Species Names and Labeling

SPECIES TYPE
Select a Species type—Bulk species, Surface species, or Solvent.

Bulk species and Solvent are solved for volumetric concentrations (SI unit: mol/m3),
while Surface species are solved for surface concentration (SI unit: mol/m2). The
compositions for Bulk species and Solvent use the syntax c_speciesname, while Surface
species uses csurf_speciesname_surf.

When Surface species is selected, the corresponding reaction formula introduces (ads)
after the species notation and changes the species’ name to speciesname_surf.
Additionally, the Species node name is updated in a similar fashion.

GENERAL PARAMETERS
The General Parameters section deals with species parameters.

102 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

Edit, if necessary, the species Molar mass M and the ionic Charge z of the species in
question.

It is possible to specify the species density ρ when the fluid Mixture is specified as Liquid.
The default value is that of water at 293 K.

REACTION RATE
Change the Automatic default setting to User defined to use a species reaction rate other
than the one set up in the associated Reaction node. For individual species, use the User
defined option to set a reaction rate other than zero (that is, non-reactive).

Edit either the Rate expression (SI unit: mol/(m3·s)), the Surface rate expression (SI
unit: mol/(m2·s)), or both. For a bulk species, both expressions appear if surface
reactions are present in the reactor since the reaction of the species can depend both
on bulk reaction R and surface reaction Rads rates. For a surface species, only the
surface reaction rate Rads appears.

ADDITIONAL SOURCE
The Additional Source section is available in order to include additional rate
contribution for the species to the reaction kinetics. When the Additional source check
box is selected, add an Additional rate expression in the text field (SI unit: mol/m3).

SPECIES CONCENTRATION/ACTIVITY
To account for non-ideality in the fluid mixture adjust the activity coefficient in the
Activity coefficient text field here. The section is only shown if activity instead of
concentration has been chosen in the interface, i.e. the Use activities check box is
selected on the Chemistry interface Settings window

Click to select the Locked concentration/activity check box if the species concentration
or activity should be treated as constant.

SPECIES TRANSPORT EXPRESSIONS

Here the required parameters to compute various transport properties can be edited.
To show this section the Calculate mixture properties check box needs to be selected
under the Calculate Transport Properties section.

• For a gas mixture, there are maximum five properties to consider: σ, the
characteristic length (unit: Å) of the Lennard-Jones/Stockmayer potential; ε/kb, the
energy minimum (SI unit: K) of the Lennard-Jones/Stockmayer potential; μD, the
dipole moment (SI unit: Debye); ki, the thermal conductivity of the gas (SI unit:

THE CHEMISTRY INTERFACE | 103

 W/(m K)); and Diffusivity of the species (SI unit: m2/s). The latter two can be set
as Automatic, when theoretical Transport Parameters expressions are available.
• For mixtures of gas with solvent, all properties above except the thermal
conductivity is shown. This is instead calculated under the Calculate mixture
properties section on the Settings window for the Chemistry interface. This requires
that the Calculate Thermodynamic Properties check box is selected on the
Chemistry interface Settings window.
• For a liquid mixture, there is only the parameter ki, the thermal conductivity (SI
unit: W/(m K)) to edit.
• For mixtures of liquid with solvent, the thermal conductivity is shown only for the
species set as Solvent.

SPECIES THERMODYNAMIC EXPRESSIONS

The parameters utilized for calculation of thermodynamic mixture and reaction
properties are set in this section. It is accessed when the Calculate Thermodynamic
Properties check box is selected on the Chemistry interface Settings window, that is,
temperature dependence is accounted for.

The Species enthalpy is by default computed with the NASA format. In this case, enter
the following to compute the species’ heat capacity, Cp (SI unit: J/(mol⋅K)), the molar
enthalpy, h (SI unit: J/mol), and the molar entropy, s (SI unit: J/(mol⋅K)):

• Lower temperature limit Tlo

• Middle temperature limit Tmid
• Upper temperature limit Thi
• Polynomial coefficients alow,k and ahi,k

Any coefficients for the thermodynamic polynomials entered into the alow,k fields
apply to the temperatures in the range Tlo to Tmid; coefficients entered into the ahi,k
fields apply to temperatures in the range Tmid to Thi range. The coefficients can also
be imported in the CHEMKIN Import for Species Property section in the Chemistry node.

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

Using the Species Node

104 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

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. The feature is typically used
when importing CHEMKIN kinetics files.

Add the node from the Chemistry toolbar or right-click Chemistry and add it from the
context menu.

For the case when reaction kinetics data are entered manually into the Reaction table
and temperature dependent reaction kinetics apply (Calculate Thermodynamic
Properties check box is selected), right-click to add a Reaction Thermodynamics
subnode or select it from the Chemistry toolbar, Attributes menu. In it, the Enthalpy of
Reaction (J/mol) for each reaction can be specified.

REACTION TABLE
The reversible reactions in the Reaction table are numbered and contain reactants,
products, and kinetic parameters describing the reaction. Use the buttons under the
Reaction table to add and sort the reaction details.

• In general, use the Move Up ( ), Move Down ( ), and Delete ( ) buttons and
the fields under tables to edit the table contents. Or right-click a table cell and select
Move Up, Move Down, or Delete.
• The Add button ( ) adds default reactant, A, and product, B, with a default. Click
the corresponding field to edit the reactant, product, or parameters. After editing
the Species Group node is also updated. It is created together with the reaction
group.
• You can save the parameters to a text file to reuse in other models. Click the Save to
File button ( ) and enter a File name in the Save to File dialog box, including the
extension.txt. Click Save to store the parameters in a text file or in a Microsoft Excel
Workbook spreadsheet if the license includes LiveLink™ for Excel®. The information
is saved in space-separated columns in the same order as displayed on screen. When
saving to Excel, an Excel Save dialog box appears where you can specify the sheet and
range and whether to overwrite existing data, include a header, or use a separate
column for units.
• You can import or load data in files from a spreadsheet program, for example, with
the Load from File button ( ) and the Load from File dialog box that appears. Data
must be separated by spaces or tabs. If there is already data in the table, imported
parameters are added after the last row. Move or edit rows as needed. If the license

THE CHEMISTRY INTERFACE | 105

 includes LiveLink™ for Excel® you can also load parameters from a Microsoft Excel
Workbook spreadsheet. Then an Excel Load dialog box appears where you can specify
the sheet and range and whether to overwrite existing data. It is also possible to
import from a spreadsheet containing a separate column for units.

In the case of twenty or more reactions the Disable updating variables during editing
table check box is available. Select this to speed up editing text fields; automatic
updates related to edits do not occur until you click to clear the check box.

CREATE REACTION AND SPECIES

Enter a reaction number in the Moving reaction (with the number) from table text field
and click Create Reaction to remove the reaction from the Reaction table to the model
tree. This introduces a reaction node named after the reaction number and species
names and simultaneously creates corresponding species nodes. This action is
powerful, since it enables all the editing possibilities available for Reaction and Species
nodes.

CHEMKIN IMPORT FOR KINETICS

Click to select the Import CHEMKIN data check box to import a CHEMKIN Kinetics
input file. To import the data directly into the table columns, click Browse to locate the
CHEMKIN file to be imported, then click Import.

CHEMKIN Data and NASA Polynomials

Equilibrium Reaction Group

The Equilibrium Reaction Group node ( ) allows for input of a large number of
equilibrium reactions in the same table. This node functions in the same way as the
Reversible Reaction Group for reversible reactions.

Add the node from the Chemistry toolbar or right-click Chemistry and add it from the
context menu.

For the case when reaction kinetics data are entered manually into the Reaction table
and temperature dependent reaction kinetics apply (Calculate Thermodynamic
Properties check box is selected), right-click to add a Reaction Thermodynamics
subnode or select it from the Chemistry toolbar, Attributes menu. In it, the Enthalpy of
Reaction (J/mol) for each reaction can be specified.

106 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

REACTION TABLE
The equilibrium reactions in the Reaction table are numbered and contain reactants,
products, and kinetic parameters describing the reaction. Use the buttons under the
Reaction table to add and sort the reaction details.

• In general, use the Move Up ( ), Move Down ( ), and Delete ( ) buttons and
the fields under tables to edit the table contents. Or right-click a table cell and select
Move Up, Move Down, or Delete.
• The Add button ( ) adds default reactant, A, and product, B, with a default. Click
the corresponding field to edit the reactant, product, or parameters. After editing
the Species Group node is also updated. It is created together with the reaction
group.
• You can save the parameters to a text file to reuse in other models. Click the Save to
File button ( ) and enter a File name in the Save to File dialog box, including the
extension.txt. Click Save to store the parameters in a text file or in a Microsoft Excel
Workbook spreadsheet if the license includes LiveLink™ for Excel®. The information
is saved in space-separated columns in the same order as displayed on screen. When
saving to Excel, an Excel Save dialog box appears where you can specify the sheet and
range and whether to overwrite existing data, include a header, or use a separate
column for units.
• You can import or load data in files from a spreadsheet program, for example, with
the Load from File button ( ) and the Load from File dialog box that appears. Data
must be separated by spaces or tabs. If there is already data in the table, imported
parameters are added after the last row. Move or edit rows as needed. If the license
includes LiveLink™ for Excel® you can also load parameters from a Microsoft Excel
Workbook spreadsheet. Then an Excel Load dialog box appears where you can specify
the sheet and range and whether to overwrite existing data. It is also possible to
import from a spreadsheet containing a separate column for units.

In the case of twenty or more reactions the Disable updating variables during editing
table check box is available. Select this to speed up editing text fields; automatic
updates related to edits do not occur until you click to clear the check box.

Chemical Vapor Deposition of GaAs: Application Library path

Chemical_Reaction_Engineering_Module/
Reactors_with_Mass_and_Heat_Transfer/gaas_cvd

THE CHEMISTRY INTERFACE | 107

 Species Group
The Species Group node ( ) contains information on a molecular level about the
volumetric species and the surface species present in the model. The Property for
Volumetric Species or Property for Surface Species tables typically collect parameters
from when importing CHEMKIN transport files.

Add the node from the Chemistry toolbar or right-click Chemistry and add it from the
context menu. This node is also automatically added when either the Reversible
Reaction Group or the Equilibrium Reaction Group are used.

For the case of temperature dependent reaction kinetics (Calculate Thermodynamic

Properties check box is selected), a Species Thermodynamics subnode is automatically
created in which the thermodynamic properties of the species can be specified.

CHEMKIN
This section allows import of CHEMKIN transport files. To import the data directly
into the table columns, click Browse to locate the CHEMKIN file to be imported, then
click Import. Note that this section is only shown when transport properties are
computed (Calculate mixture properties check box under the Calculate Transport
Properties is selected).

CHEMKIN Data and NASA Polynomials

Reaction Thermodynamics
The Reaction Thermodynamics subnode ( ), the Enthalpy of Reaction (J/mol) of
each reaction can be specified. This node overrides all the automatically calculated
reaction enthalpies as defined in the Species Thermodynamics subnode.

Add the Reaction Thermodynamics node from the Chemistry toolbar, Attributes menu.
Alternatively, when the Calculate Thermodynamic Properties check box is selected on
the Chemistry interface Settings window, right-click a Reversible Reaction Group or
Equilibrium Reaction Group to add the Reaction Thermodynamics subnode.

108 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

Species Activity
The Species Activity node ( ) creates variables for the activities of all the species/
surface species present in the Species Group parent feature. Edit the Activity coefficient
field in the Species Activity or Surface Species Activity tables by clicking in these.

Species Activity is a subnode to the Species Group node. It is automatically generated

when non-ideality in the fluid mixture is accounted for; when the Use activity check
box is selected in the Activity section.

Species Thermodynamics
The Species Thermodynamics node ( ) creates variables for the enthalpies, entropies,
and heat capacities for all the species/surface species present in the Species Group
parent feature. The purpose is to compute thermodynamic mixture properties and the
heat of reactions.

This node is a subnode to the Species Group node when the Calculate
Thermodynamic Properties check box is selected on the Chemistry interface Settings
window.

SPECIES THERMODYNAMICS PROPERTY

Select a Type selection for the thermodynamic properties. The NASA format alternative
requires the setting of several polynomial constants and is typically used together with
CHEMKIN import. The User defined alternative only requires input of Species molar
enthalpy (J/mol) and Species molar capacity (J/(mol·K)).

CHEMKIN IMPORT FOR THERMODYNAMIC DATA

This section allows import of thermodynamic CHEMKIN transport files. To import
the data directly into the table columns, click Browse to locate the CHEMKIN file to
be imported, then click Import. Note that this can only be done for the NASA format
option.

• CHEMKIN Data and NASA Polynomials

THE CHEMISTRY INTERFACE | 109

 S t udy S te ps f or t h e R eac t i on
Engineering Interface
Reactor Types and Solver Study Steps
The predefined CSTR, Batch and Semibatch reactor types available in the Reaction
Engineering interface set up equations describing how species concentrations in a
perfectly mixed system change with time. Time Dependent is the correct study type to
use for these reactor types. The simulation time is specified in the settings of the Time
Dependent study step.

The predefined Plug flow reactor type sets up equations for stationary conditions
describing how species molar flow rates (SI unit: mol/s) vary with the reactor volume.
Stationary Plug Flow is the correct study type to use for this reactor type. The reactor
volume is specified in the Stationary Plug Flow study step feature

Note that selecting the Reaction Engineering interface and the Time Dependent study sets
up the Batch, constant volume reactor type by default. The Time Dependent study is also
suitable for all CSTR reactors and the Semibatch reactor. However, if the reactor type is
changed to Plug flow, then the Time Dependent study step needs to be replaced with
a Stationary Plug Flow step. Combining a Reaction Engineering interface with the
Stationary Plug Flow study does not set up a Plug flow reactor type by default. In that
situation, the Plug Flow reactor type needs to be set manually in the Reaction
Engineering interface.

Solver Study Steps for Parameter Estimation

Parameter Estimation calculations are enabled in the Study branch, by right-clicking
the study node and selecting the Optimization study step from the context menu.
Moving to the main Study node and clicking Compute starts the parameter estimation.

110 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES

The Optimization Solver node is a subnode to the Solver node. In the settings window
the Optimization Solver section offers the several methods for solving the optimization
problem.

Figure 2-9: The settings for the Optimization Solver are accessed in the Study tree.

www.comsol.com/optimization-module

STUDY STEPS FOR THE REACTION ENGINEERING INTERFACE | 111

112 | CHAPTER 2: THE CHEMISTRY AND REACTION ENGINEERING INTERFACES
 3

Chemical Species Transport Interfaces

The Chemical Species Transport branch ( ) includes a number of subbranches to

describe mass transport and chemical reactions. The physics interfaces are
summarized in the first section, and then described in detail throughout this
chapter. All physics interfaces include features for defining arbitrary reaction
kinetics, to be used as mass sources and sinks, as well as arbitrary mass transport
parameters.

• Overview of Chemical Species Transport Interfaces

• Theory for the Transport of Diluted Species Interface and the other transport
interfaces.
• 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 Nernst-Planck Equations Interface
• The Nernst-Planck-Poisson Equations Interface
• The Electrophoretic Transport Interface
• The Surface Reactions Interface

113
 • The Reacting Flow Multiphysics Interface
• The Reacting Flow in Porous Media Multiphysics Interface

Note that The Chemistry and Reaction Engineering Interfaces and The Chemistry
Interface are described in The Chemistry and Reaction Engineering Interfaces chapter.

114 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

Overview of Chemical Species
T r a ns po r t Interfaces
In this section:

• Available Physics Interfaces

• Coupling to Other Physics Interfaces
• Adding a Chemical Species Transport Interface and Specifying the Number of
Species

Available Physics Interfaces

THE SURFACE REACTIONS (SR) INTERFACE

The Surface Reactions Interface ( ) models reactions involving surface adsorbed
species and species in the bulk of a reacting surface. The physics interface is typically
active on a model boundary and is coupled to a mass transport physics interface active
on a model domain. The Surface Reactions interface can be used together with other
Chemical Species Transport interfaces, the Reacting Flow interfaces, and the
Electrochemistry interfaces. Predefined expressions for the growth velocity of the
reacting surface makes it easy to set up models with moving boundaries. Also see the
Theory for the Surface Reactions Interface.

The Electrochemistry interfaces require the addition of the Batteries &

Fuel Cells Module, the Corrosion Module, the Electrochemistry Module,
or the Electrodeposition Module.

THE TRANSPORT OF DILUTED SPECIES AND TRANSPORT OF DILUTED

SPECIES IN POROUS MEDIA (TDS) INTERFACES
The mass transfer equations account for chemical species transport by diffusion,
convection, and migration due to an electric field (electrokinetic flow)—either alone
or in combination. The Transport of Diluted Species Interface ( ) is an enhanced
version of the physics interface included with the basic COMSOL Multiphysics license
and is applicable for solutions (either fluid or solid) where the transported species have
concentrations at least one order of magnitude less than the solvent. The settings for
this physics interface can be chosen so as to simulate chemical species transport

OVERVIEW OF CHEMICAL SPECIES TRANSPORT INTERFACES | 115

 through diffusion (Fick’s law), convection (when coupled to fluid flow), and migration
(when coupled to an electric field — electrokinetic flow).

The Transport of Diluted Species in Porous Media Interface ( ) is tailored for the
modeling of solute transport in porous media. The physics interface supports cases
where either the solid phase substrate is exclusively immobile, or when a gas-filling
medium is also assumed to be immobile.

THE TRANSPORT OF CONCENTRATED SPECIES (TCS) INTERFACE

The Transport of Concentrated Species Interface ( ) is used for modeling transport
within mixtures where no one component is clearly dominant. Often the
concentrations of the participating species are of the same order of magnitude, and the
molecular effects of respective species on each other needs to be considered. This
physics interface supports transport through Fickian diffusion, a mixture-average
diffusion model, and as described by the Maxwell-Stefan equations. These take into
account the diffusion properties of all species with respect to each other. Convective
transport and transport by migration in electric fields are also accounted for by this
physics interface. Also see the Theory for the Transport of Diluted Species Interface.

THE NERNST-PLANCK EQUATIONS (NPE) INTERFACE

The Nernst-Planck Equations Interface ( ) includes a migration term, along with
convection and diffusion mass transport, together with an equation that guarantees
electroneutrality. A term to describe the electric potential is also provided in the physics
interface itself. Also see the Theory for the Nernst-Planck Equations Interface.

THE REACTING FLOW IN POROUS MEDIA (RFP) INTERFACES

The Reacting Flow in Porous Media, Transport of Diluted Species Interface ( )
(found under the Chemical Species Transport>Reacting Flow in Porous Media branch
( ) when adding a physics interface), is a multiphysics interface treating diluted
reacting mixtures transported by a porous media flow. The component coupling for
the velocity field is set up automatically.

The Reacting Flow in Porous Media, Transport of Concentrated Species

Interface( ) found under the Chemical Species Transport>Reacting Flow in Porous
Media branch ( ) when adding a physics interface), is a multiphysics interface
treating concentrated reacting mixtures transported by a porous media flow. The
couplings between velocity field and mixture density are set up automatically.

116 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

The next sections, Coupling to Other Physics Interfaces and Adding a Chemical
Species Transport Interface and Specifying the Number of Species provide more
information to help you start modeling.

Coupling to Other Physics Interfaces

When using this module you are often simulating applications that can be described by
the mass transport interfaces in the Chemical Species Transport branch. Yet, as a lot of
mass transport is dependent on convection, couplings to Fluid Flow interfaces are
required. COMSOL Multiphysics and the Chemical Reaction Engineering Module
include physics interfaces for laminar flow as well as porous media flow. More advanced
descriptions of fluid flow, such as turbulent flow and multiphase flow, require the CFD
Module.

Most chemical reactions or other type of material processing, such as casting, either
require or produce heat, which in turn affects both the reaction and other physical
processes connected to the system. Heat transfer through conduction and convection,
when flow is laminar, as well as through porous media are supported in this module.
More extensive description of heat transfer, such as in turbulent flow or involving
radiation, require the Heat Transfer Module. The Heat Transfer Module also includes
turbulent flow.

COMSOL Multiphysics easily supports simulations of electrostatics or DC-based

physical phenomena, even if conductivity is nonlinear. If the electric field is AC/DC in
nature, or if the system is affected by electromagnetic waves, then the AC/DC Module
and RF Module have appropriate physics interfaces for these phenomena. Some
applications of electrochemical reactions, particularly in electrochemical power source
applications, are better handled by the Batteries & Fuel Cells Module.

Adding a Chemical Species Transport Interface and Specifying the

Number of Species
A chemical species transport interface can be added when first creating a new model,
or at any time during the modeling process.

Creating a New Model in the COMSOL Multiphysics Reference Manual

OVERVIEW OF CHEMICAL SPECIES TRANSPORT INTERFACES | 117

 1 To add a physics interface:
- Select New to open the Model Wizard, after selecting a space dimension, go to the
Select Physics page.
- From the Home toolbar click Add Physics ( ). Or right-click the Component
node in the Model Builder and select Add Physics. Go to the Add Physics window.

2 Under Chemical Species Transport, navigate to the physics interface to add and
double-click it.
There are other ways to add a physics interface depending on whether you are in the
Model Builder or Add Physics window:
- In the Model Wizard, click Add or right-click and select Add Physics ( ). The
physics interface displays under Added physics interfaces.
- In the Add Physics window, click Add to Component ( ) or right-click and select
Add to Component.
3 Specify the number of species (concentrations or mass fractions) and the names:
- In the Model Wizard, on the Review Physics Interface page under Dependent
Variables.
- In the Add Physics window, click to expand the Dependent Variables section.
- After adding the physics interface, you can also edit this information—click the
node in the Model Builder, then, on the Settings window under Dependent
Variables, specify the information.

4 Continue by adding more physics interfaces and specifying the number of species
(concentrations or mass fractions) that are to be simulated in a mass transport
interface when adding that interface.
5 In the Dependent Variables section, enter the Number of species. To add a single
species, click the Add Concentration button ( ) underneath the table or enter a
value into the Number of species field. Click the Remove Concentration button ( )
underneath the table if required.
6 The Transport of Concentrated Species interface and the Nernst-Planck Equations
interface both need to contain at least two species (the default). Also edit the strings
or names directly in the table. The names must be unique for all species (and all
other dependent variables) in the model.
7 For the Nernst-Planck Equations interface, an electric potential variable is also
required.

118 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

The Reaction Engineering interface can automatically set up the reacting
species and their dependent variables. If you plan on using chemistry from
the Reaction Engineering interface in species transport interface, the
Generate Space Dependent Model feature is recommended to set up the
transport interface.

OVERVIEW OF CHEMICAL SPECIES TRANSPORT INTERFACES | 119

 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 small
compared to a solvent fluid or solid. As a rule of thumb, a mixture containing several
species can be considered dilute when the concentration of the solvent is more than
90 mol%. Due to the dilution, mixture properties such as density and viscosity can be
assumed to correspond to those of the solvent.

When studying mixtures that are not dilute, the mixture and transport properties
depend on the composition, and a different physics interface is recommended. See The
Transport of Concentrated Species Interface 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 Sources for Species Transport

Migration • Solving a Diffusion Equation Only
• Convective Term Formulation • Supporting Electrolytes
• Crosswind Diffusion • Theory for the Reactive Pellet Bed
• Danckwerts Inflow Boundary • References
Condition
• Equilibrium Reaction Theory
• Mass Balance Equation

120 | CHAPTER 3: 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 (3-1)
∂t

Equation 3-1 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)

The mass flux diffusive flux vector

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 (3-2)

An input field for the diffusion coefficient is available. Anisotropic diffusion tensor
input is supported.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 121

 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 3-1 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 3-1), 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.

122 | CHAPTER 3: 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.

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.
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.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 123

 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 (a check box to activate
migration is available) and implements the mass balance equation in Equation 3-1.

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 (3-3)
∂t

∂c
conservative: ----- + ∇ ⋅ ( cu ) = ∇ ⋅ J i + R (3-4)
∂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.

Solving a Diffusion Equation Only

Remove the convection term from Equation 3-3 and Equation 3-4 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

124 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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

Note: The features below are only available in a limited set of add-on products. For a
detailed overview of which features are available in each product, visit
http://www.comsol.com/products/specifications/

POINT SOURCE
·
A point source is theoretically formed by assuming a mass injection/ejection, Q c (SI
3
unit: mol/(m ·s)), in a small volume δV and then letting the size of the volume tend
to zero while keeping the total mass flux constant. Given a point source strength, q· p,c
(SI unit: mol/s), this can be expressed as

· ·
lim
δV → 0  Qc = qp,c (3-5)
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 3-5, Q c must tend
to plus or minus infinity as δV tends to zero. This means that in theory the
concentration also tends to plus or minus infinity.

Observe that “point” refers to the physical representation of the source. A point source
can therefore only be added to points in 3D components and to points on the
symmetry axis in 2D axisymmetry components. Other geometrical points in 2D
components represent physical lines.

The finite element representation of Equation 3-5 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

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 125

 the source. A finer mesh gives a smaller affected region but also a more extreme
concentration value. It is important not to mesh too finely around a point source since
this can result in unphysical concentration values. It can also have a negative effect on
the condition number for the equation system.

LINE SOURCE
·
A line source can theoretically be formed by assuming a source of strength Q l,c (SI
3
unit: mol/(m ·s)), located within a tube with cross section δS and then letting δS tend
to zero while keeping the total mass flux per unit length constant. Given a line source
strength, q· l,c (SI unit: mol/(m·s)), this can be expressed as

·
lim  Ql,c = q· l,c (3-6)
δS → 0
δS

As in the point source case, an alternative approach is to assume that mass is injected/
extracted through the surface of a small object. This results in the same mass source,
but requires that effects resulting from the physical object’s volume are neglected.

The weak contribution

q· l,c test ( c )

is added on lines in 3D or at points in 2D (which represent cut-through views of lines).

Line sources can also be added on the axisymmetry line in 2D axisymmetry
components. It cannot, however, be added on geometrical lines in 2D since those
represent physical planes.

As with a point source, it is important not to mesh too finely around the line source.

For feature node information, see Line Mass Source and Point Mass
Source in the COMSOL Multiphysics Reference Manual.

126 | CHAPTER 3: 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 Batteries & Fuel Cells 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
http://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 (3-7)
∂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 | 127

 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.

128 | CHAPTER 3: 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 (3-8)
j

Equation 3-8 is simply Ohm’s law for ionic current transport and can be simplified to

i = – κ ∇φ (3-9)

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 3-9, yields:

∇ ⋅ ( – κ ∇φ ) = 0 (3-10)

Equation 3-10 can be easily solved using the Electrostatics or Secondary Current
Distribution interface and, when coupled to the Transport in Diluted Species interface,
the potential distribution shows up in the migration term.

Crosswind Diffusion
Transport of diluted species applications can often result in models with a very high
cell Péclèt number—that is, systems where convection or migration dominates over
diffusion. Streamline diffusion and crosswind diffusion are of paramount importance
to obtain physically reasonable results. The Transport of Diluted Species interface

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 129

 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 Péclèt number is very high and the model contains
many thin layers, such as contact discontinuities. You then have three options:

• Refine the mesh, especially in regions with thin layers.

• Use a nonlinear solver with a constant damping factor less than one.
• Switch to the Codina crosswind formulation.

CODINA
The Codina formulation is described in Ref. 1. It adds diffusion strictly in the direction
orthogonal to the streamline direction. Compared to the do Carmo and Galeão
formulation, the Codina formulation adds less diffusion but is not as efficient at
reducing over- and undershoots. It also does not work as well for anisotropic meshes.
The advantage is that the resulting nonlinear system is easier to converge and that
underresolved gradients are less smeared out.

Danckwerts Inflow Boundary Condition

Constraining the composition to fixed values at an inlet to a reactor may sometimes
result in issues with unreasonably high reaction rates or singularities at the inlet
boundary. These problems may many times be mitigated by using a flux boundary
condition instead, based on the inlet concentrations and the fluid velocity. In chemical
engineering, this type of flux boundary condition is also known as a Danckwerts
condition.

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

Given an inlet concentration ci,0, the Danckwerts inflow boundary condition reads

n ⋅ ( J i + uc i ) = n ⋅ ( uc i, 0 ) (3-11)

130 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

See further:

Inflow

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:

∂ θc ∂
( i ) + ∂ ( ρc P, i ) + (a v c G, i) + u ⋅ ∇c i =
∂t ∂t ∂t (3-12)
∇ ⋅ [ ( D D, i + D e, i ) ∇c i ] + R i + S i

On the left-hand side of Equation 3-12, 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 3-12 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 θ; the matrix (drained) density, ρ = (1 − εp)ρp,
and the solid phase density ρp.

For saturated porous media, the liquid volume fraction θ is equal to the porosity εp,
but for partially saturated porous media, they are related by the saturation s as θ = sεp.
The resulting gas volume fraction is av = εp − θ = (1-s)εp.

On the right-hand side of Equation 3-12, 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 3-12 describe production or
consumption of the species; Ri is a reaction rate expression which can account for

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 131

 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.

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 – ρc P, i (3-13)
( P, i ) = ρ – ρc P, i ∂ 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 ∂a v ∂c i ∂a v
∂a = av + k G, i c i = a v k G, i + k G, i c i (3-14)
v c G, i ∂ ci ∂ t ∂t ∂ t ∂t
∂t

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

SATURATED POROUS MEDIA

In the case of transport in a saturated porous medium, θ = 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 (3-15)
∂t p i ∂t

Convection in Porous Media

Convection describes the movement of a species, such as a pollutant, with the bulk
fluid velocity. The velocity field u corresponds to a superficial volume average over a
unit volume of the porous medium, including both pores and matrix. This velocity is
sometimes called Darcy velocity, and defined as volume flow rates per unit cross

132 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

section of the medium. This definition makes the velocity field continuous across the
boundaries between porous regions and regions with free flow.

The velocity field to be used in the Model Inputs section on the physics
interface can, for example, be prescribed using the velocity field from a
Darcy’s Law or a Brinkman Equations interface.

The average linear fluid velocities ua, provides an estimate of the fluid velocity within
the pores:

u
u a = ----- Saturated
εp
u
u a = ---- Partially saturated
θ

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

Figure 3-1: A block of a porous medium consisting of solids and the pore space between the
solid grains. The average linear velocity describes how fast the fluid moves within the pores.
The Darcy velocity attributes this flow over the entire fluid-solid face.

CONVECTIVE TERM FORMULATION

The Transport of Diluted Species in Porous Media interface includes two formulations
of the convective term. The conservative formulation of the species equations in
Equation 3-12 is written as:

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 133

 ∂ ( θc ) + ∂ ( ρ c ) + ∂ (a c ) + ∇ ⋅ uc =
∂t i
∂ t b P, i ∂ t v G, i i
(3-16)
∇ ⋅ [ ( 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 3-12.

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. Depending on the transport of diluted species occurs
in free flow, saturated or partially saturated porous media, the effective diffusivity is
defined as:

De = DF Free Flow
εp
D e = ----- D L Saturated Porous Media
τL
θ
D e = ----- D L Partially Saturated Porous Media
τL
θ av
D e = ----- D L + ------ k G D G Partially Saturated with Volatilization
τL τG

Here DF, DL, and DG are the single-phase diffusion coefficients for the species diluted
in fluid, pure liquid and gas phases 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

134 | CHAPTER 3: 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 = θ ε , τG = av ε

and Bruggeman model

–5 ⁄ 2 2 –5 ⁄ 2 2
τL = θ ε , τG = av ε

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

–1 ⁄ 3
τL = εp

and for the Bruggeman model the tortuosity is defined as

–1 ⁄ 2
τL = εp

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

Dispersion
The contribution of dispersion to the mixing of species typically overshadows the
contribution from molecular diffusion, except when the fluid velocity is very small.

The spreading of mass, as species travel through a porous medium is caused by several
contributing effects. Local variations in fluid velocity lead to mechanical mixing
referred to as dispersion occurs because the fluid in the pore space flows around solid
particles, so the velocity field varies within pore channels. The spreading in the
direction parallel to the flow, or longitudinal dispersivity, typically exceeds the
transverse dispersivity from up to an order of magnitude. Being driven by the
concentration gradient alone, molecular diffusion is small relative to the mechanical
dispersion, except at very low fluid velocities.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 135

 Figure 3-2: Spreading of fluid around solid particles in a porous medium.

is controlled through the dispersion tensor DD. The tensor components can either be
given by user-defined values or expressions, or derived from the directional
dispersivities.

Using the longitudinal and transverse dispersivities in 2D, the dispersivity tensor
components are (Ref. 9):

2 2
ui uj
D Dii = α L ------- + α T -------
u u

ui uj
D Dij = D Dji = ( α L – α T ) -----------
u

In these equations, DDii (SI unit: m2/s) are the principal components of the
dispersivity tensor, and DDji and DDji are the cross terms. The parameters αL and αT
(SI unit: m) specify the longitudinal and transverse dispersivities; and ui (SI unit: m/
s) stands for the velocity field components.

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:

136 | CHAPTER 3: 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 (3-17)
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 3-17 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 three predefined relationships to predict the solid
concentrations, cPi from the concentration in the liquid phase, ci:

∂c P
cP = KP c k P = -------- = K P User defined
∂c
c N ∂c P cP
c P = K F  -------- k P = -------- = N ------ Freundlich (3-18)
 c ref ∂c c
KL c ∂c P K L c Pmax
c P = c Pmax -------------------- k P = -------- = ---------------------------2- Langmuir
1 + KL c ∂c ( 1 + KL c )

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 137

 The above equations contains the following parameters:

• User defined isotherm KP (SI unit: m3/kg).

• 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).

• These predefined expressions are adsorption isotherms that describe the amount of
species sorbed to the solid. Defined at equilibrium, the switch between liquid and
solid phases is instantaneous.

Using a Species Source feature, arbitrary expressions can be entered to define, for
example, nonequilibrium and temperature-dependent adsorption laws, including
those set out by Fetter (Ref. 7) and Bear and Verruijt (Ref. 8).

The retardation factor, RF, describes how adsorption slows the solute velocity, uc,
relative to the average linear velocity of the fluid, ua, as in

ρ b ∂c P ua
RF = 1 + ------ -------- = ------
θ ∂c uc

If the contaminant moves at the average linear velocity of the fluid for RF = 1. For
RF > 1, the contaminant velocity is smaller than the fluid velocity owing to residence
time on solids.

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.

138 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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 3-12. 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 (3-19)
∂t ∂t

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

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

∇c i = ∇ n c i + ∇ t c i

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

∇c i = ∇ t c i

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 139

 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 3-19. See The Transport of Diluted Species in Fractures
Interface for more information about the physics interface solving the
equation on boundaries only.

Theory for the Reactive Pellet Bed

The Reactive Pellet Bed, available to users of the Chemical Reaction Engineering
Module, adds to the Transport of Diluted Species interface a domain feature that can
simulate regions filled with reactive catalyst pellets, as in packed bed reactors. The
pellets are simulated with the Extra Dimension technology provided by the COMSOL
software: A 1D, 2D, or 3D domain represents the bed volume. The extra dimension
is the added radial microscale dimension inside each pellet.

For an example of how to use the Reactive Pellet Bed, see the model
example A Multiscale 3D Packed Bed Reactor, file path
Chemical_Reaction_Engineering_Module/Reactors_with_Porous_Catalysts/
packed_bed_reactor_3d

140 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

 Outflow

Macroscale: c
Concentration in
fluid passing through
bed

Microscale:
cpe Concentration
in porous pellet
Inflow

Pellet of radius rpe

Figure 3-3: Schematic showing the macroscale (bed volume) and the microscale (pellet).

The transport and reaction equations inside the pellets are solved on an extra
dimension attached to the 1D, 2D, or 3D physics interfaces, including axisymmetric
cases.

The equations inside the spherical pellet are solved as a spherical transport equations
on a nondimensional radial coordinate on the domain 0-1. A given pellet size or a
discrete distribution of sizes can be used.

The model equations assume spherical particles (pellets) of a radius rpe. Modeling
assumptions for cylinders, flakes, and user-defined shapes can also be used. Consider
the microscale concentration cpe inside an individual porous pellet or pellets, and the
macro-concentration c in the packed bed gas volume.

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 141

 The pellet radius input can be:

• One uniform pellet radius, which can be space dependent f (x, y, z).
• Binary, ternary, and so on, mix up to 5 radii. The user inputs a table with the mix of
sizes (1 mm, 2 mm, for example), and a percentage of each. Different chemical
reactions per pellet size can be specified.

The model equation for the bulk (macroscale) species is, for example:

∂
ε b (c i) + u ⋅ ∇c i + ∇ ⋅ ( – D b, i ∇c i ) = R i (3-20)
∂t

• The dependent variable c for each chemical species i represents the interstitial
concentration (SI unit: mol/m3), that is, the physical concentration based on unit
volume of fluid flowing between the pellets.
• εb is the bed porosity (SI unit: 1). It should be noted that the R term on the right
side is per unit volume of bed, (SI unit: mol/(m3· s)).

Looking inside a pellet: Assuming no concentration variations in the space-angle (θ, ϕ)

direction, but only in the radial (r) direction of the spherical pellet allows a spherically
symmetric reaction-diffusion transport equation inside the pellet. If rdim (SI unit: m)
is the spatial radial coordinate in the pellet, and rpe is the pellet radius, the
nondimensional coordinate r = rdim/rpe can be defined. The modeling domain on r
goes from 0 to 1.

0 (center) r_pe (pellet perimeter)

0 1

Figure 3-4: Modeling domain in a pellet for dimensional (top) and nondimensional
(bottom) coordinates.

A shell mole balance across a spherical shell at radius rdim (SI unit: m), and a
subsequent variable substitution r = rdim/rpe gives the following governing equation
inside the pellet on the domain 0<r<1:

142 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

  2 2 ∂ 2 2 2 
4πN  r r pe ε pe (c pe, i) + ∇ ⋅ ( – r D pe, i ∇c pe, i ) = r r pe R pe, i  (3-21)
 ∂ t 

where

• N is the number of pellets per unit volume of bed.

• Equally as in Equation 3-21, cpe is the interstitial (physical) species concentration in
moles/m3 of fluid volume element inside the pore channel,
• Rpe is the reaction rate in moles/(m3· s) of pellet volume. It should be stressed that
the user input of R is per unit volume of pellet.
The effective diffusion coefficient in Equation 3-20 and Equation 3-21 depends on
the porosity εpe, tortuosity τ, and physical gas diffusivity D in the porous pellet
generally as

ε pe D
D pe = ------------ .
τ

The available tortuosity models for porous media are the Millington and Quirk
(Ref. 12),

–1 ⁄ 3 4⁄3
τ = ε pe  D pe = ε pe D, (3-22)

Bruggeman,

–1 ⁄ 2 3⁄2
τ = ε pe  D pe = ε pe D (3-23)

and the Tortuosity model, where the tortuosity expression is entered as user input:

ε pe D
D pe = ------------ (3-24)
τ

These are readily used for both gaseous and liquid fluids along with various types of
pellet shapes. For instance, the first model has been shown to fit mass transport in
soil-vapor and soil-moisture well.

Equation 3-21 can be solved for two types of boundary conditions at the interface
between the pellet surface and the fluid in this feature.

• Continuous concentration: assuming that all resistance to mass transfer to/from the
pellet is within the pellet and no resistance to pellet-fluid mass transfer is on the bulk
fluid side. The concentration in the fluid will thus be equal to that in the pellet pore

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 143

 just at the pellet surface: c pe,i = c i . This constraint also automatically ensures flux
continuity between the internal pellet domain and the free fluid domain through
so-called reaction forces in the finite element formulation.
• Film resistance (mass flux): The flux of mass across the pellet-fluid interface into the
pellet is possibly rate determined on the bulk fluid side by film resistance. The
resistance is expressed in terms of a film mass transfer coefficient, hDi, such that:
N i,inward = h D, i ( c i – c pe, i ) , (3-25)

where Ni, inward is the molar flux from the free fluid into a pellet and has the unit
moles/(m2· s).

With the film resistance formulation above, the free fluid Equation 3-20 needs to be
amended for flux continuity so that

∂
ε b (c i) + u ⋅ ∇c i + ∇ ⋅ ( – D b, i ∇c i ) = R i – N i,inward S b (3-26)
∂t

where Sb (SI unit: m2/m3) is the specific surface area exposed to the free fluid of the
packed bed (not including the inside of the pores).

For the case of randomly packed spherical pellets, the specific surface area exposed to
the free fluid is (Ref. 3):

3
S b = ------- ( 1 – ε b ) (3-27)
r pe

The mass transfer coefficient in Equation 3-25 can be computed from the fluid
properties and flow characteristics within the porous media. For this, the Sherwood,
Sh, number defined as the ratio between the convective mass transfer coefficient and
the diffusive mass transfer coefficient is often used:

hL
Sh = --------
D

where L is a characteristic length (for spheres, typically the radius), and D is the
diffusion coefficient in the fluid. From the Sherwood number definition, the mass
transfer coefficient can be computed.

Three commonly used empirical expressions for the calculation of the Sherwood
number are the Frössling relation (Ref. 4):

1⁄2 1⁄3
Sh = 2 + 0.552Re Sc , (3-28)

144 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

which was measured on pellets in the size region 1 mm, the Rosner relation (Ref. 5)

0.4 1⁄2 2⁄3

Sh = Sc ( 0.4Re + 0.2Re ), (3-29)

and the Garner and Keey relation (Ref. 4)

1⁄2 1⁄3
Sh = 0.94Re Sc , (3-30)

which was measured for Re numbers greater than 250.

All three depend on the Reynolds, Re, and Schmidt, Sc, numbers. The first describing
the fluid flow regime (laminar versus turbulent) and the second, the ratio between the
viscous diffusion rate and the molecular (mass) diffusion rate. In the expressions,
properties such as velocity, u, dynamic viscosity, μ, and density, ρ, of the fluid are
included.

ρuL
Re = -----------
μ

μ
Sc = --------
ρD

SURFACE SPECIES
Surface species corresponds to species bound to the solid interface of the porous pellet,
which is also in contact with the bulk fluid. The surface species hence only exists within
the pellet. The surface species are assumed immobile, and the concentration is only
dependent on the surface reaction rate:

∂c pe,s
= R pe,s (3-31)
∂t

It can be noted that there is no mass flux of surface species within the pellet or across
the pellet outer surface and the bulk fluid.

NONSPHERICAL PARTICLES
For nonspherical pellets (of any shape), the relations above can be applied
approximately by reinterpreting the pellet radius rpe as

V pe
r pe = 3 --------- (3-32)
A pe

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 145

 (Ref. 14), where Vpe and Ape are the volume and external surface, respectively, of a
single pellet of any shape. Since the specific surface Spe (SI unit: m2/m3) of one pellet
is defined as

A pe
S pe = ---------
V pe

it follows by insertion of Equation 3-32 that

3
S pe = ------- .
r pe

For a packed bed of which the packing has a porosity εb, the specific surface of the bed
will be

A pe
S b = S pe ( 1 – ε b ) = --------- ( 1 – ε b )
V pe

or

3
S b = ------- ( 1 – ε b ) (3-33)
r pe

for any pellet shape. Now rpe and Sb can be calculated for any shape and inserted in
equations Equation 3-21 and Equation 3-26. Some common specific shapes have
automatic support:

Cylinders
For cylindrical shapes, applying Equation 3-32 gives

2
V pe πr cyl L cyl 1
r pe = 3 --------- = 3 -------------------------------------------------
- = -------------------------------
-. (3-34)
A pe 2 2 2 -
2πr cyl L cyl + 2πr cyl ------------ + ------------
3r cyl 3L cyl

It is common practice to assume that the top and bottom surface of cylindrical pellets
have negligible effect on the mass transfer to and from the internals of the pellet, or,
r cyl « L cyl . Equation 3-34 then simplifies to

3
r pe = --- r cyl
2

and Equation 3-33 to

146 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

 2
S b = -------- ( 1 – ε b )
r cyl

Flakes
The derivation for a disc-shaped catalyst pellet is exactly the same as for cylindrical
pellets, except that the assumption is reversed about the end surfaces and the envelope
surface: r flake » w flake , where wflake is the thickness of the disc. This gives

3
r pe = --- w flake
2

and

2
S b = -------------- ( 1 – ε b ) .
w flake

SURFACE REACTION
Surface reactions can also be simulated inside the pellet. Surface species are introduced
into pellet by adding them in the Surface Species section of the Reactive Pellet Bed
feature.

A bulk species can take part in both volumetric and surface reactions. The total
reaction rate for a bulk species within a pellet is defined as:

R = R pe + R pe,s ⋅ S b,reac

Here Rpe is the reaction rate for bulk reactions occurring inside the pellet. Rpe,s and
Sb are the reaction rate and the reactive specific surface area for a surface reaction
occurring inside the pellet, on the interface between the solid matrix and the fluid.

HEAT SOURCE
The heat source of endothermic or exothermic reactions inside the pellet needs to be
accounted for in the heat transfer on the bulk level. Thermal equilibrium is assumed in
each pellet, implying that the heat balance is not solved within the pellet. To account
for the heat evolution in the bulk, the source is averaged across the pellet:

 Qpe dV
Q bed = V
--------------------- ( 1 – ε b ) W/m3
V pe

If there are multiple pellet sizes i in the bed the heat source computed by summing
over all sizes:

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 147

 pct i
Q bed =   Qbed, i ⋅ ---------
100
-
i

Here pcti is the volume percentage of pellet i in the pellet mix.

References
1. R. Codina, “A discontinuity-capturing crosswind-dissipation for the finite element
solution of the convection-diffusion equation”, Computer Methods in Applied
Mechanics and Engineering, vol. 110, pp. 325–342, 1993.

2. P.V. Danckwerts, “Continuous flow systems: Distribution of residence times”,

Chem. Eng. Sci., vol. 2, no. 1, 1953.

3. J.M. Coulson and J.F. Richardson, Chemical Engineering, vol. 2, 4th ed.,
Pergamon Press, Oxford, U.K., 1991.

4. J.M. Coulson and J.F. Richardson, Chemical Engineering, vol. 1, 4th ed.,
Pergamon Press, Oxford, U.K., 1991.

5. D.E Rosner, Transport Processes in Chemically Reacting Flow Systems, ISBN-13:

978-1483130262, Butterworth-Heinemann, 1986

6. D.M. Mackay, D.L. Freyberg, P.V. Roberts, and J.A. Cherry, “A Natural Gradient
Experiment on Solute Transport in a Sand Aquifer: 1. Approach and Overview of
Plume Movement”, Water Resourc. Res., vol. 22, no. 13, pp. 2017–2030, 1986.

7. C.W. Fetter, Contaminant Hydrogeology, Prentice Hall, 1999.

8. J. Bear and A. Verruijt, Modeling Groundwater Flow and Pollution, D. Reidel

Publishing, 1994.

9. J. Bear, Hydraulics of Groundwater, McGraw-Hill, 1979.

10. R.D. Burnett and E.O. Frind, “An Alternating Direction Galerkin Technique for
Simulation of Groundwater Contaminant Transport in Three Dimensions: 2.
Dimensionality Effects”, Water Resour. Res., vol. 23, no. 4, pp. 695–705, 1987.

11. J. Bear, Dynamics of Fluids in Porous Media, Elsevier Scientific Publishing, 1972.

12. R.J. Millington and J.M. Quirk, “Permeability of Porous Solids”, Trans. Faraday
Soc., vol. 57, pp. 1200–1207, 1961.

13. I. Langmuir, “Chemical Reactions at Low Temperatures”, J. Amer. Chem. Soc.,

vol. 37, 1915.

148 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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

THEORY FOR THE TRANSPORT OF DILUTED SPECIES INTERFACE | 149

 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 3-100 then describes the mass transport for an individual species:

∂
( ρω i ) + ∇ ⋅ ( ρω i u ) = – ∇ ⋅ j i + R i (3-35)
∂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 3-36 for
the conservation of mass

150 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

 ∂ρ
+ ∇ ⋅ ( ρu ) = 0 (3-36)
∂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 (3-37)
∂t

Q − 1 of the species equations are independent and possible to solve for using
Equation 3-37. To compute the mass fraction of the remaining species, COMSOL
Multiphysics uses the fact that the sum of the mass fractions is equal to 1:

ω1 = 1 –  ωi (3-38)
i=2

Multicomponent Gas Diffusion: Maxwell-Stefan Description

In a multicomponent mixture, the mass flux relative to the mass average velocity, ji,
can be defined by the generalized Fick equations (Ref. 1):

 D̃ik dk – Di ∇ ln T
T
j i = – ρω i (3-39)
k=1

In Equation 3-39:
˜
• 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)

THEORY FOR THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 151

 Q
1
d k = -------------- ∇p k – ω k ∇p – ρ k g k + ω k
cR g T  ρl gl (3-40)
l=1

where

• c (SI unit: mol/m3) is the total molar concentration

• Rg is the universal gas constant 8.314 J/(mol·K)
• p (SI unit: Pa) is the total pressure
• pk (SI unit: Pa) is the partial pressure, and
• 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 3-39 and Equation 3-40, the total diffusive flux for the
species depends on the gradients of all species concentrations, temperature, and
pressure as well as any external force on the individual species.

Using the ideal gas law, p = c·Rg·T, and the definition of the partial pressures, pk = xkp,
the equation can be written as

Q
1
d k = ∇x k + --- ( x k – ω k ) ∇p – ρω k g k + ω k
p  ρωl gl (3-41)
l=1

The mole fraction xk is given by

ωk
x k = -------- M (3-42)
Mk

and the mean molar mass M (SI unit: kg/mol) by

Q
1- ωi
----
M
=  ------
Mi
-
i=1

152 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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 
(3-43)
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 3-43. The
diffusivities are symmetric

˜ ˜
D ik = D ki

and are related to the multicomponent Maxwell-Stefan diffusivities, Dik, through the
following relation (Ref. 2)

xi xk
 ( adjB i ) jk
j≠i ˜ –D ˜ ,
---------- = – ω i ω k ---------------------------------------- , ( B ) = D kj ij i≠j (3-44)
D ik ˜ i kj
 D ij ( adjB i ) jk
j≠i

where (adjBi)jk is the jkth component of the adjoint of the matrix Bi.

For low-density gas mixtures, the multicomponent Maxwell-Stefan diffusivities, Dij,

can be replaced with the binary diffusivities for the species pairs that are present.

Solving for Equation 3-44 leads to a number of algebraic expressions for each of the
components in the multicomponent Fick diffusivity matrix. For two- and
three-component systems, these are implemented and solved directly by COMSOL
˜
Multiphysics. For instance, the component D 12 in a ternary system is given by:

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

THEORY FOR THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 153

 For four components or more, COMOL 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 (3-45)
ij ij
˜
where ij are indices in the matrices D and N, and ranges from 1 to the number of
species, Q.

The elements of the matrix N in Equation 3-45 are defined as

–1
N ij = ( P ) ij (3-46)

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 3-45 is a scalar value that provides numerical stability and
should be of the same order of magnitude as the multicomponent Maxwell-Stefan
diffusion coefficients. The physics interface therefore defines q as the sum of the
multicomponent Maxwell-Stefan diffusion coefficients:

n–1
 n 
g =   
 D ij 

i = 1  j = i+1 

This definition for g works well in most cases. In rare cases, it might be
necessary to change the value to obtain convergence.

154 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

Because the multicomponent Fick diffusivity matrix is symmetric, it is sufficient to
˜
apply Equation 3-46 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 --------- (3-47)
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 3-47 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 3-47 together with the Maxwell-Stefan equations, where isobaric and
isothermal conditions have been assumed, the following expression for the
mixture-averaged diffusion coefficients can be derived (Ref. 3):

m 1 – ωi
D i = -------------------------- (3-48)
xk

N
---------
k≠iD
ik

If instead the diffusive flux (relative to the mass averaged velocity) is assumed
proportional to the mass fraction gradient, the mass flux is defined as:

m* ∇ω i m*
j md, i = – ρ i D i ---------- = – ρD i ∇ω i (3-49)
ωi

THEORY FOR THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 155

 For this assumption, using Equation 3-49 together with the Maxwell-Stefan
equations, also assuming isobaric and isothermal conditions, the following expression
for the mixture-averaged diffusion coefficients can be derived (Ref. 3):

1 xk xi ωk
k ≠ i --------
D ik 1 – ω i k ≠ i D ik
N N
----------- = - + --------------- --------- (3-50)
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 ρωi ( ud,i + uc ) =
N
j md, i = 0 (3-51)

Hence the correction velocity is:

i = 1 ωi ud,i
N
uc = – (3-52)

Here ud,i is the diffusion velocity resulting from the flux assumption in Equation 3-47
or Equation 3-49. Note that the correction velocity is a constant correction (same for
all species), but varies in space.

Using the correction velocity together with Equation 3-47, 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 (3-53)
M M i

156 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

If instead Equation 3-49is used the resulting diffusive flux is

i = 1 Di
m* N m*
j md, i = – ρD i ∇ω i + ρω i ∇ω i (3-54)

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 --------- (3-55)
xi

when assuming that the diffusive flux is proportional to the mole fraction gradient. If
instead assuming that it is proportional to the mass fraction it becomes

F
j md, i = – ρD i, kl ∇ω i (3-56)
F
In the equations above D i, kl represents a general diffusion matrix (SI unit: m2/s)
describing the diffusion of species i into the mixture. This form makes it possible to
use any diffusion coefficient, matrix, or empirical model based on Fick’s law. For
example, in situations when the mass transport is not dominated by diffusion, an
alternative is to use the diffusion coefficients at infinite dilution,

F 0
D i, kk = D i

THEORY FOR THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 157

 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 (3-57)
M M i, kl i

when using Equation 3-55 and

i = 1 Di, kl ∇ωi
F N F
j md, i = – ρD i, kl ∇ω i + ρω i (3-58)

when instead using Equation 3-56.

When using the Fick’s Law approximation, Additional Transport Mechanisms can be
accounted for in the same manner as described above for the mixture-averaged
approximation.

Multicomponent Thermal Diffusion

Mass diffusion in multicomponent mixtures due to temperature gradients is referred
to as the Soret effect. This occurs in mixtures with high temperature gradients and
large variations in molecular weight (or size) of the species. Typically species with high
molecular weight accumulate in lower temperature regions while the diffusion due to
the Soret effect transports species with low molecular weight to higher temperature
regions. In COMSOL Multiphysics, thermal diffusion is included by prescribing the
T
thermal diffusion coefficients D i . In a multicomponent mixture, the sum of the
thermal diffusion coefficients is zero:

 Di
T
= 0
i=1

Regularization of Reaction Rate Expression

The flexibility of COMSOL means that a reaction can result in nearly any reaction rate
contribution Ric to a mass fraction 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
feature in Transport of Concentrated Species Interface contains a way to regularize
make the rate expression contributions comply to these restrictions.

158 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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 ) (3-59)
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 3-59 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 3-59 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.

4. A. Soulaïmani and M. Fortin, “Finite Element Solution of Compressible Viscous

Flows Using Conservative Variables”, Computer Methods in Applied Mechanics and
Engineering, vol. 118, pp. 319–350, 1994.

THEORY FOR THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 159

 Theory for the Electrophoretic
Transport Interface
The Electrophoretic Transport Interface models transport of charged and uncharged
species, and in addition sets up a charge balance equation for the electrolyte potential.

The species concentrations are denoted, ci (SI unit: mol/m3), and the potential, φ l
(SI unit: V).

The species are transported by diffusion, migration, and (optionally) convection

according the Nernst-Planck set of equations. The total flux of species i is denoted Ni
(SI unit: mol/(m2·s)) according to

N i = – D i ∇c i – z i u m, i Fc i ∇φ l + uc i = J i + uc i (3-60)

where Di (m2/s) is the diffusion coefficient, zi (1) the corresponding charge, um,i (SI
unit: s·mol/kg) the mobility and u (SI unit: m/s) the velocity vector. Ji denotes the
molar flux relative to the convective transport (SI unit: mol/(m2·s)). For a detailed
description of the theory of these equations and the different boundary conditions, see
Theory for the Transport of Diluted Species Interface.

CHARGE BALANCE EQUATION

2
The current vector, il (A/m ), is defined as

il =  zi Ni (3-61)
i

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

The governing equation for the electrolyte potential is

∇ ⋅ il = Ql (3-62)

where Ql (A/m3) is the electrolyte current source stemming from, for example,
porous electrode reactions. For non-porous electrode domains this source term is
usually zero.

PROTON AND HYDROXIDE CONCENTRATIONS AND ELECTRONEUTRALITY

Assuming the total number of species to be N+2, the assumption of electroneutrality is

160 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

 N+2

 zi ci = 0 (3-63)
i=1

In water-based systems the species H+ and OH- are always present. The auto
ionization reaction for water is

+ -
H 2 O ↔ H + OH (3-64)

This reaction is fast, following the equilibrium relation

2 –6
c H + c OH - = K w × 1 mol dm (3-65)

– 14
where K w ≈ 10 .

Now, the electroneutrality condition, including the two additional species H+ and
OH-, reads

c H + – c OH - +  zi ci = 0 (3-66)
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 (3-67)
2 4

and

2
Σ Σ 2 –6
c OH - = --- + ------ + K w × 1 mol dm (3-68)
2 4

where

Σ =  zi ci (3-69)
i=1

MASS BALANCE EQUATIONS FOR DISSOCIATION SPECIES

Assume a set of species Si describing k dissociation steps from

THEORY FOR THE ELECTROPHORETIC TRANSPORT INTERFACE | 161

 + z +k–1
z +k z +k–1 + [ H ] [ S k0– 1 ]
S k0 ↔ S k0– 1 +H K a, 1 = ----------------------------------------
z0 + k
(3-70)
[ Sk ]

to

+ z
z +1 z + [ H ] [ S 00 ]
S k0 ↔ S 00 + H K a, k = -------------------------
z +1
- (3-71)
[ S 10 ]

where z0 is the charge (valence) of species S0 (which has no dissociable protons) and
Ka,j is the acid (equilibrium) constant of the jth dissociation reaction. The brackets [ ]
here represents the species activity. The charge of each species is always deductible from
the index i according to z0+i and will be dropped from now on.

If the proton activity is known, any species Sm may be expressed using any other species
Sl according to

m–l
[H] [ Sl ]
[ S m ] = -------------------------------------
k–l
(3-72)

∏ K a, j
j = k–m+1

if m>l and

k–m
m–l
[ Sm ] = [ H ] [ Sl ] ∏ K a, j
j = k–l+1
(3-73)

if l>m.

Setting m=i and denoting the flux of species i by Ni using equation Equation 3-60,
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 (3-74)
δt

where Req,i,j is the reaction source stemming from the jth dissociation step (with
Req,i,k+1=0), and Ri any additional reaction sources.

The reaction source contributions from the dissociation steps are generally not known,
but may be canceled by taking the sum of all mass balance equations, resulting in

162 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

 k k
δc i
 ------ 
 -
 δt + ∇ ⋅ N i =  Ri (3-75)
i=0 i=0

AVERAGE IONIZATION FORMULATION FOR LARGE MOLECULES

Large protein molecules are typically subject to a large number of dissociation steps.

As an alternative way to a long chain of dissociation steps for describing protein

transport, one can instead formulate the protein transport based on the average
number of protons 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 (3-76)

and similarly the addition to the charge neutrality condition is zc i .

When considering the contribution to the current and the charge balance equation one
2 2
needs to take into account that the squared average charge, z = ( z 0 – 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 ) (3-77)

The average number of protons removed from the proton typically depends on the
pH. If the average number of removed protons depend only on the pH, the averaged
squared number of protons removed can be written as

2 d ν ν2
ν = – c H+ + (3-78)
d cH+

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

2 d ν z2 d z z2
z = – cH+ + = – cH+ + (3-79)
d c H+ d cH+

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

kT
r = --------------- (3-80)
6πμD

THEORY FOR THE ELECTROPHORETIC TRANSPORT INTERFACE | 163

 where is the μ (Pa·s) is the dynamic viscosity and k the Boltzmann constant.

For small molecules, one frequently uses the Nernst-Einstein relation between the
diffusivity and the mobility

D
u m = -------- (3-81)
RT

For larger molecules, such as proteins, the mobility may instead be calculated based on
the Debye-Hückel-Henry expression (Ref. 2 ) according to

ef ( κr ) Df ( κr )
u m = ------------------------------------ = ------------------------------ (3-82)
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 = ----------------- (3-83)
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 + (3-84)
εε 0 kT  
 i=1 i = N–M+1 

REFERENCES
1 The Dynamics of Electrophoresis, Mosher, Saville and Thormann, VCH
Verlagsgesellschaft mbH, Weinheim, Germany, 1992.

164 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

2 Computer Simulation and Experimental Validation of the Electrophoretic
Behavior of Proteins. 2. Model Improvement and Application to Isotachophoresis,
Mosher, Gebauer, Caslavska, and Thormann. Analytical Chemistry, vol. 64,
pp. 2991–2997, 1992.

THEORY FOR THE ELECTROPHORETIC TRANSPORT INTERFACE | 165

 Theory for the Surface Reactions
Interface
The Surface Reactions Interface solves for an arbitrary number of surface
concentrations, cs,i (SI unit: mol/m2), referring to species adsorbed on a reactive
surface, and an arbitrary number of bulk concentrations cb,k (SI unit: mol/m3),
referring to the species in the solid material that constitutes the bulk of the reactive
surface.

In this section:

• Governing Equations for the Surface Concentrations

• Governing Equations for the Bulk Concentrations
• ODE Formulations for Surface Concentrations
• Surface Reaction Equations on Deforming Geometries
• Reference for the Surface Reactions Interface

Governing Equations for the Surface Concentrations

Transport of adsorbed species occurs in the tangential direction along the surface. The
Surface Reactions interface models the tangential flux in the surface dimension, the
surface molar flux, Nt,i (SI unit: mol/(m·s)) (the subscript t refers to the tangential
direction), as governed by diffusion according to Fick’s law:

N t, i = – D s , i ∇ t c s , i

where Ds,i (SI unit: m2/s) is the surface diffusion coefficient for species i.

The governing equation for the surface concentrations is written as:

∂c s, i
= – ∇ t ⋅ N t, i + R s , i (3-85)
∂t

where Rs,i (SI unit: mol/(m2·s)) is the sum of all sources due to surface reactions and
adsorption/desorption phenomena.

Of frequent interest for surface reaction kinetics are the fractional surface coverages, θi
(dimensionless), of the species (with index i).

166 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

Writing the density of sites of the surface as Γs (SI unit: mol/m2) and the site
occupancy number for each species as σi (dimensionless), the surface coverages can be
calculated from:

σ i c s, i
θ i = --------------
Γs

(The site occupancy number accounts for the situation when a large species covers
more than one site on the surface.)

For the case of monolayer adsorption, the sum of all fractional coverages of free and
adsorbed sites is unity, and hence the fraction of free sites on the surface, θ*, can be
calculated from:

θ* = 1 –  θi
i

Governing Equations for the Bulk Concentrations

BULK SPECIES RATES AND GROWTH VELOCITY

The reaction rate for a bulk species of index k, being added to the bulk due to surface
reactions is defined as Rb,k (SI unit: mol/(s·m2)).

The reaction rate in mass basis, rb,k (SI unit: kg/(s·m2)) for species k, is given by:

r k = M k R b, k

with Mk (SI unit: kg/mol) being the molar mass of the species.

Based on this, the species contribution to the bulk growth velocity, vk (SI unit: m/s),
is given by:

r b, k
v b, k = ----------
ρk

where ρk is the species density (SI unit: kg/m3).

TOTAL RATES AND VELOCITY

To get the corresponding total values, a summation for all bulk species is made
according to:

THEORY FOR THE SURFACE REACTIONS INTERFACE | 167

 R b, tot =  R b, k
k

r b, tot =  r b, k
k

v b, tot =  vb, k
k

FRACTIONAL RATES AND VELOCITY

The fractional deposition rates are calculated by:

R b, k
R b, frac, k = ---------------
R b, tot

r b, k
r b, frac, k = -------------
r b, tot

v b, k
v b, frac, k = --------------
v b, tot

The fractional deposition rates can be used as measures of the local

fractional composition in a deposited layer at a certain thickness or time.

ACCUMULATED BULK QUANTITIES

By solving for the bulk species concentrations for each time step, the accumulated mass
and thickness changes of the bulk material can be calculated.

The bulk concentration, cb,k (SI unit: mol/m2), for species k is governed by the
equation:

∂c b, k
= R b, k (3-86)
∂t

The bulk concentration in mass basis, mb,k (SI unit: kg/m2) for a species k, can be
derived from:

m b, k = M k c b, k

168 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

leading to the bulk thickness sb,k (SI unit: m) of species k according to:

m b, k
s b, k = -------------
ρk

TOTAL BULK QUANTITIES

The total bulk concentration is calculated according to:

c b, tot =  c b, k
k

The deposited total mass, mb,tot (SI unit: kg/m2) is

m b, tot =  mb, k
k

and the total bulk thickness, stot (SI unit: m) is

s b, tot =  sk
k

FRACTIONAL QUANTITIES
The fractional bulk concentration, bulk mass, and thickness (all dimensionless) are
calculated according to:

c b, k
c b, frac, k = -------------
c b, tot

m b, k
m b, frac, k = ----------------
m b, tot

s b, k
s b, frac, k = -------------
s b, tot

ODE Formulations for Surface Concentrations

The surface of a 1D geometry has a 0 dimension, hence no surface transport can be
modeled and the governing equation is reduced to an ODE:

THEORY FOR THE SURFACE REACTIONS INTERFACE | 169

 ∂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 3-85
and Equation 3-86, respectively.

– c s, i ∂ ln ∂ A
∂t

– c b, k ∂ ln ∂ A
∂t

where ∂A is the infinitesimal mesh area segment (area scale factor). The above terms
account for the concentration change due to a fractional area change.

Second, the resulting unwanted tangential convection, imposed by the mesh

movement, is compensated for by the adding following terms to the right-hand side of
Equation 3-85 and Equation 3-86, respectively:

∇ t ⋅ ( c s, i v t, mesh )

∇ t ⋅ ( c b, k v t, mesh )

170 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

where vt,mesh is the mesh velocity in the tangential direction.

This convectional term needs often to be stabilized using methods such as streamline
diffusion or isotropic diffusion.

Reference for the Surface Reactions Interface

1. R.J. Kee, M.E. Coltrin, and P. Glarborg, Chemically Reacting Flow, chapter 11,
John Wiley & Sons, 2003.

THEORY FOR THE SURFACE REACTIONS INTERFACE | 171

 Theory for the Nernst-Planck
Equations Interface
The Nernst-Planck Equations Interface theory is described in this section:

• Governing Equations for the Nernst-Planck Formulation

• Convective Term Formulation

Governing Equations for the Nernst-Planck Formulation

The following version of the Nernst-Planck equation treats transport by convection,
diffusion, and migration of each dissolved species:

∂c i
+ ∇ ⋅ ( c i u ) = – ∇ ⋅ ( – D i ∇c i – u m, i F c i ∇V ) + R i = – ∇ ⋅ J i + R i (3-87)
∂t

where Ji is the molar flux relative to the convective transport, and Ri (SI unit: mol/
(m3 ·s)) is the reaction term. The velocity, u, is equal to the velocity of the solvent.
This implies that the solute’s contribution to the solvent’s velocity, through shear or
any other forces, is negligible in comparison to the solvent’s contribution to the solute.
Equation 3-87 introduces one variable for the concentration of each of the dissolved
species and the electric potential, V.

Apart from the transport equations, the physics interface assumes that the
electroneutrality condition holds:

 zi ci = 0 (3-88)

that is that the net charge in every control volume is zero. This means that Q − 1,
where Q is the number of species present, can be solved for using Equation 3-87. The
remaining species concentration is computed from the electroneutrality condition.
This means that boundary conditions for this species cannot be specified, although it
takes part in the boundary condition descriptions for the current density. Often, the
species chosen to be computed from electroneutrality is the oppositely charged ion, to
the electroactive species, from a supporting electrolyte.

172 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

To compute the electric potential, taking the transport of every charged species into
account, create the following linear combination of the n mass balance equations,
where each mass balance equation is weighted with the factor Fzi:

n
∂c i  n  n

F  zi
∂t

+ ∇ ⋅ F 
z N 
i i = F zi Ri  (3-89)
i=1  i=1  i=1

The first term in Equation 3-89 is zero, which can be shown by taking the time
derivative of the electroneutrality condition. The expression under the divergence
operator is the total current density vector, defined by:

i = F  z i ( – D i ∇c i – z i u m , i F c i ∇V ) (3-90)
i=1

Notice that no convective term is included in the expression for the current density,
which is also a result of the electroneutrality condition.

It is now possible to rewrite Equation 3-89 as:

∇⋅i = F  zi Ri (3-91)
i=1

This equation states the conservation of electric charge and is the one solved for to
compute the electric potential.

Equation 3-87, Equation 3-88, and Equation 3-91 are sufficient for describing the
potential and concentration distribution in an electrochemical cell or in an electrolyte
subjected to an electric field.

A useful observation from Equation 3-90 is that the ionic conductivity, defined in
absence of concentration gradients, is implicitly given by:

κ = F
2
 z2i ci um, i
i=1

Furthermore, the potential gradient caused by the presence of a concentration

gradient under situations with zero current becomes:

THEORY FOR THE NERNST-PLANCK EQUATIONS INTERFACE | 173

 n

 ( –Di ∇ci )
i=1
∇V = ------------------------------------
n

 zi um, i Fci
i=1

In the field of electrochemistry, this is known as the junction potential.

Convective Term Formulation

When modeling mass transport in the Nernst-Planck Equations interface, two
formulations are available for the convective term: a conservative and a
nonconservative formulation. Equation 3-87 shows the conservative formulation.

In the nonconservative formulation the velocity is moved out of the divergence

operator, which improves the stability of systems coupled to a momentum balance
(fluid-flow equation). This is only applicable to systems that contain incompressible
fluids. In these fluids, the following continuity equation is satisfied:

∇⋅u = 0 (3-92)

and Equation 3-87 can be rewritten as:

∂c i
+ ∇ ⋅ ( – D i ∇c i – z i u m, i Fc i ∇V ) + u ⋅ ∇c i = R i (3-93)
∂t

which can be called the nonconservative formulation and is the default formulation in
the Nernst-Planck Equations interface.

Specify the equation formulation in the Advanced Settings section of the

Nernst-Planck Equations interface.

174 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

Theory for the Reacting Laminar
Flo w Inte r f a c e
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 Pseudo Time Stepping for
Laminar Flow Models 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 LAMINAR FLOW INTERFACE | 175

 n ⋅ ( j i + ρω i u ) = r s,i M i (3-94)

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 (3-95)
i=1

referred to as the Stefan velocity, here denoted us. To reach Equation 3-95 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 3-95 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 ) (3-96)

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.

176 | CHAPTER 3: 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 = ------------------------------------
- (3-97)
N
 
ρ  1 –  ω i, 0
 i 

Using a Reacting Flow interface, the Stefan velocity, defined in the manner of
Equation 3-97, 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 Reaction
feature (in Transport of Concentrated Species), the default (Automatic) reaction rate
used by the Reaction feature is based on the mass action law. Consider a general
reaction belonging to a set of j reactions and involving i species:

f (3-98)
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 (3-99)
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 LAMINAR FLOW INTERFACE | 177

 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).

178 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

The Transport of Diluted Species
Interface
The Transport of Diluted Species (tds) interface ( ), found under the Chemical Species
Transport branch ( ), is used to calculate the concentration field of a dilute solute in
a solvent. Transport and reactions of the species dissolved in a gas, liquid, or solid can
be handled with this interface. The driving forces for transport can be diffusion by
Fick’s law, convection when coupled to a flow field, and migration, when coupled to
an electric field.

The interface supports simulation of transport by convection and diffusion in 1D, 2D,
and 3D as well as for axisymmetric components in 1D and 2D. The dependent variable
is the molar concentration, c. Modeling multiple species transport is possible, whereby
the physics interface solves for the molar concentration, ci, of each species i.

SETTINGS
The Label is the default physics interface name.

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

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

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

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

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 179

 Note: Some of the additional transport mechanisms listed below are available in all
products. For details see http://www.comsol.com/products/specifications/.

• By default, the Convection check box is selected. Clear the check box to disable
convective transport.
• Select the Migration in electric field check box to activate transport of ionic species in
an electric field. See further the theory section Adding Transport Through
Migration.

Transport of ionic species in an electric field is available in a limited set of

add-on products. See http://www.comsol.com/products/
specifications/ for more details on availability.

Mass Transport in Porous Media

The Mass transport in porous media check box activates functionality specific to species
transport in porous media. When selected, the following transport mechanisms are
available:

• Select the Dispersion in porous media check box to activate the dispersion mechanism
in porous media. See further Dispersion in the theory chapter.
• Select the Volatilization in partially saturated porous media check box to model
volatilization in partially saturated domains. See further Theory for the Transport of
Diluted Species Interface.

The following features are also enabled when selecting the Mass transport in porous
media check box:

• Adsorption
• Fracture
• Partially Saturated Porous Media
• Porous Media Transport Properties
• Reactive Pellet Bed

180 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

CONSISTENT STABILIZATION
To display this sections, click the Show button ( ) and select Stabilization.

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

INCONSISTENT STABILIZATION
To display this section, click the Show button ( ) and select Stabilization. By default,
the Isotropic diffusion check box is not selected, because this type of stabilization adds
artificial diffusion and affects the accuracy of the original problem. However, this
option can be used to get a good initial guess for underresolved problems.

ADVANCED SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.
Normally these settings do not need to be changed. Select a Convective term—
Nonconservative form (the default) or Conservative form. The conservative formulation
should be used for compressible flow. See Convective Term Formulation for more
information.

DISCRETIZATION
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

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 181

 is checked, the solver computes variables storing accurate boundary fluxes from each
boundary into the adjacent domain.

If the check box is cleared, the COMSOL Multiphysics software instead computes the
flux variables from the dependent variables using extrapolation, which is less accurate
in postprocessing results but does not create extra dependent variables on the
boundaries for the fluxes.

The flux variables affected in the interface are:

• ndflux_c (where c is the dependent variable for the concentration). This is the
normal diffusive flux and corresponds to the boundary flux when diffusion is the
only contribution to the flux term.
• ntflux_c (where c is the dependent variable for the concentration). This is the
normal total flux and corresponds to the boundary flux plus additional transport
terms, for example, the convective flux when you use the nonconservative form.

Also the Apply smoothing to boundary fluxes check box is available if the previous check
box is checked. The smoothing can provide a more well-behaved flux value close to
singularities.

For details about the boundary fluxes settings, see Computing Accurate Fluxes in the
COMSOL Multiphysics Reference Manual.

The Value type when using splitting of complex variables setting should in most pure
mass transfer problems be set to Real, which is the default. It makes sure that the
dependent variable does not get affected by small imaginary contributions, which can
occur, for example, when combining a Time Dependent or Stationary study with a
frequency-domain study. For more information, see Splitting Complex-Valued
Variables in the COMSOL Multiphysics Reference Manual.

DEPENDENT VARIABLES
The dependent variable name is the Concentration c by default. The names must be
unique with respect to all other dependent variables in the component.

Add or remove species variables in the model and also change the names of the
dependent variables that represent the species concentrations.

Enter the Number of species. Use the Add concentration ( ) and Remove
concentration ( ) buttons as needed.

182 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

FURTHER READING

• Theory for the Transport of Diluted Species Interface

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

• Effective Diffusivity in Porous Materials: Application Library path

COMSOL_Multiphysics/Diffusion/effective_diffusivity
• Micromixer: Application Library path COMSOL_Multiphysics/
Fluid_Dynamics/micromixer

The Transport of Diluted Species in Porous Media Interface

This interface ( ), found under the Chemical Species Transport branch ( ), is used
to calculate the species concentration and transport in free and porous media. The
interface is the same as the Transport of Diluted Species interface but it uses other
defaults: The Mass Transport in Porous Media property is selected, and a Porous
Media Transport Properties node is added by default. The interface includes reaction
rate expressions and solute sources for modeling of species transport and reaction in
porous media.

This interface is dedicated to modeling transport in porous media, including immobile

and mobile phases, where the chemical species may be subjected to diffusion,
convection, migration, dispersion, adsorption, and volatilization in porous media. It
supports cases where either the solid phase substrate is exclusively immobile, or when
a gas-filling medium is also assumed to be immobile.

It applies to one or more diluted species or solutes that move primarily within a fluid
that fills (saturated) or partially fills (unsaturated) the voids in a solid porous medium.
The pore space not filled with fluid contains an immobile gas phase. Models including
a combination of porous media types can be studied.

The main feature nodes are the Porous Media Transport Properties and Partially
Saturated Porous Media nodes, which add the equations for the species concentrations

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 183

 and provide an interface for defining the properties of the porous media, as well as
additional properties governing adsorption, volatilization, dispersion and diffusion,
migration, and the velocity field to model convection.

The physics interface can be used for stationary and time-dependent analysis.

When this physics interface is added, these default nodes are also added to the Model
Builder — Porous Media Transport Properties, No Flux (the default boundary condition),
and Initial Values. Then, from the Physics toolbar, add other nodes that implement, for
example, boundary conditions, reaction rate expressions, and species sources. You can
also right-click Transport of Diluted Species in Porous Media to select physics features
from the context menu.

SETTINGS
The rest of the settings are the same as The Transport of Diluted Species Interface.

FURTHER READING

• Theory for the Transport of Diluted Species Interface

• Domain, Boundary, and Pair Nodes for the Transport of Diluted
Species Interface

• Variably Saturated Flow and Transport — Sorbing Solute:

Application Library path Subsurface_Flow_Module/Solute_Transport/
sorbing_solute
Web link: http://www.comsol.com/model/
variably-saturated-flow-and-transport-sorbing-solute-490

Domain, Boundary, and Pair Nodes for the Transport of Diluted

Species Interface
The Transport of Diluted Species Interface has the following domain, boundary, and
pair nodes, listed in alphabetical order, available from the Physics ribbon toolbar

184 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

(Windows users), Physics context menu (Mac or Linux users), or by right-clicking to
access the context menu (all users).

To add a node, go to the Physics toolbar, no matter what operating system

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

• Adsorption • Periodic Condition

• Concentration • Point Mass Source
• Electrode Surface Coupling • Porous Electrode Coupling
• Equilibrium Reaction • Porous Media Transport Properties
• Fast Irreversible Surface Reaction • Reaction Coefficients
• Flux • Reactions
• Flux Discontinuity • Reactive Pellet Bed
• Fracture • Species Source
• Inflow • Surface Reactions
• Initial Values • Surface Equilibrium Reaction
• Line Mass Source • Symmetry
• Mass-Based Concentrations • Thin Diffusion Barrier
• No Flux • Thin Impermeable Barrier
• Open Boundary • Transport Properties
• Outflow • Turbulent Mixing
• Partially Saturated Porous Media • Volatilization
• Partition Condition

Some features require certain add-on modules. See details http://

www.comsol.com/products/specifications/

For axisymmetric components, COMSOL Multiphysics takes the axial

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

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 185

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

Transport Properties
The settings in this node are dependent on the check boxes selected under Transport
Mechanisms on the Settings window for the Transport of Diluted Species interface. It
includes only the sections required by the activated transport mechanisms. It has all the
equations defining transport of diluted species as well as inputs for the material
properties.

When the Convection check box is selected, the Turbulent Mixing subnode is available
from the context menu as well as from the Physics toolbar, Attributes menu.

MODEL INPUTS
The temperature model input is always available. Select the source of the Temperature.
For User defined, enter a value or expression for the temperature in the input field. This
input option is always available.

You can also select the temperature solved for by a Heat Transfer interface added to
the model component. These physics interfaces are available for selection in the
Temperature list.

CONVECTION
If transport by convection is active, the velocity field of the solvent needs to be
specified. Select the source of the Velocity field. For User defined, enter values or
expressions for the velocity components in the input fields. This input option is always
available.

You can also select the velocity field solved for by a Fluid Flow interface added to the
model component. These physics interfaces are available for selection in the Velocity
field list.

DIFFUSION
Select an option from the Material list. This selection list can only be used if a material
has been added in the Materials node and if that material has a diffusion coefficient
defined. Else, you need to type in the diffusivity in the User Defined edit field.

186 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

Enter the Diffusion coefficient Dc for each species. This can be a scalar value for isotropic
diffusion or a tensor describing anisotropic diffusion. Select the appropriate tensor
type — Isotropic, Diagonal, Symmetric, or Anisotropic that describes the diffusion
transport, and then enter the values in the corresponding element (one value for each
species).

Note that multiple species, as well as Migration in Electric fields (described below) is
only available for certain COMSOL Multiphysics add-on products. See details: http:/
/www.comsol.com/products/specifications/.

MIGRATION IN ELECTRIC FIELD

This section is available when the Migration in electric field check box is selected. From
the Electric potential list, select the source of the electric field.

• Enter a value or expression for the Electric potential V, which is User defined; this
input option is always available.
• Select the electric potential solved by an AC/DC-based interface that has also been
added to the model.
• Select the electric potential defined or solved by Electrochemistry interface that has
been added to the component.

By default the Mobility is set to be calculated based on the species diffusivity and the
temperature using the Nernst-Einstein relation. For User defined, and under Mobility,
select the appropriate scalar or tensor type — Isotropic, Diagonal, Symmetric, or
Anisotropic — and type in the value of expression of the mobility um,c.

Enter the Charge number zc (dimensionless, but requires a plus or minus sign) for each
species.

The temperature (if you are using mobilities based on the Nernst-Einstein relation) is
taken from Model Inputs section.

Note that the migration in electric fields feature is only available in some COMSOL
products. See details: http://www.comsol.com/products/specifications/.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 187

 EXAMPLE MODELS

• Separation Through Dialysis: Application Library path

Chemical_Reaction_Engineering_Module/Mixing_and_Separation/dialysis
Web link: http://www.comsol.com/model/
separation-through-dialysis-258

• Transport in an Electrokinetic Valve: Application Library path

Microfluidics_Module/Fluid_Flow/electrokinetic_valve
Web link: http://www.comsol.com/model/electrokinetic-valve-603

Turbulent Mixing
Use this node to account for the turbulent mixing of the chemical species caused by
the eddy diffusivity. This node should typically be used when the specified velocity field
corresponds to a RANS solution.

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

http://www.comsol.com/products/specifications/ for more details on
availability.

The subnode can added from the context menu (right-click the Transport Properties
parent node), as well as from the Physics toolbar, Attributes menu, provided that
Convection is selected as a transport mechanism.

TURBULENT MIXING PARAMETERS

Some physics interfaces provide the turbulent kinematic viscosity, and these appear as
options in the Turbulent kinematic viscosity νT list. The list always contains the User
defined option where any value or expression can be entered.

The default Turbulent Schmidt number ScT is 0.71 (dimensionless).

FURTHER READING
See the section About Turbulent Mixing in the CFD Module User’s Guide (this link
is available online or if you have the CFD Module documentation installed).

188 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

Initial Values
The Initial Values node specifies the initial values for the concentration of each species.
These serve as an initial guess for a stationary solver or as initial conditions for a
transient simulation.

DOMAIN SELECTION
If there are several types of domains with different initial values defined, it might be
necessary to remove some domains from the selection. These are then defined in an
additional Initial Values node.

INITIAL VALUES
Enter a value or expression for the initial value of the Concentration or concentrations,
ci. This also serves as a starting guess for stationary problems.

Mass-Based Concentrations
Use the Mass-Based Concentrations node to add postprocessing variables for mass-based
concentrations (SI unit: kg/m3) and mass fractions (dimensionless) for all species.

MIXTURE PROPERTIES
The default Solvent density ρsolvent is taken From material. For User defined, enter a
value or expression manually. Define the Molar mass of each species, which is needed
to calculate the mass-based concentration.

Reactions
Use the Reactions node to account for the consumption or production of species
through chemical reactions. Define the rate expressions as required.

DOMAIN SELECTION
From the Selection list, choose the domains on which to define rate expression or
expressions that govern the source term in the transport equations.

Several reaction nodes can be used to account for different reactions in different parts
for the modeling geometry.

REACTION RATES
Add a rate expression R (SI unit: mol/(m3·s)) for species i. Enter a value or expression
in the field. Note that if you have the Chemistry interface available, provided with the

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 189

 Chemical Reaction Engineering Module, the reaction rate expressions can be
automatically generated and picked up using the drop-down menu. For an example,
see the application Fine Chemical Production in a Plate Reactor as linked below.

REACTING VOLUME
This section is only available when the Mass Transport in Porous Media property is
available and selected. See http://www.comsol.com/products/specifications/ for
more details on availability.

When specifying reaction rates for a species in porous media, the specified reaction rate
may have the basis of the total volume, the pore volume, or the volume of a particular
phase.

• For Total volume, the reaction expressions in mol/(m3·s) are specified per unit
volume of the model domain (multiplied by unity).
• For Pore volume, the reaction expressions in mol/(m3·s) are specified per unit
volume of total pore space. The reaction expressions will be multiplied by the
domain porosity, εp. (εp equals unity for nonporous domains.)
• For Liquid phase, the reaction expressions in mol/(m3·s) are specified per unit
volume of liquid in the pore space. The expressions will be multiplied by the liquid
volume fraction θ. (θ equals εp for Saturated Porous Media domains).
• For Gas phase, the expressions are multiplied by the gas volume fraction av = εp − θ.
av equals 0 for Saturated Porous Media domains.

FURTHER READING
See the theory chapter on chemical species transport, starting with the section Mass
Balance Equation.

• Fine Chemical Production in a Plate Reactor: Application Library

path Chemical_Reaction_Engineering_Module/
Reactors_with_Mass_and_Heat_Transfer/plate_reactor
Web link: http://www.comsol.com/model/
fine-chemical-production-in-a-plate-reactor-8589

190 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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

–n ⋅ Ji = 0

Inflow
Use this node to specify all species concentrations at an inlet boundary.

If you want to specify the concentration of a subset of the partaking species, this can
be done by using the Concentration node instead.

For the Electroanalysis interface, this node is available when you select the Convection
check box on the physics interface Settings window.

CONCENTRATION
For the concentration of each species c0,c (SI unit: mol/m3), enter a value or
expression.

BOUNDARY CONDITION TYPE

This section in the settings is only available for some products. Search for “Inflow” on
the page: http://www.comsol.com/products/specifications/ for more details on
availability.

The option Concentration constraint constrains the concentration values on the

boundary by the use of pointwise constraints. The other option, Flux (Danckwerts) can
be more stable and fast to solve when high reaction rates are anticipated in the vicinity
of the inlet. Oscillations on the solutions can also be avoided in such cases. The latter
condition uses a flux boundary condition based on the velocity across the boundary
and the concentration values. See further details in the theory section.

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.
You can find details about the different constraint settings in the section Constraint
Reaction Terms in the COMSOL Multiphysics Reference Manual.

FURTHER READING
See the theory chapter in the section Danckwerts Inflow Boundary Condition.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 191

 Outflow
Apply this condition at outlets boundaries where species should be transported out of
the model domain by fluid motion or by an electric field (in the case of ions). It is
assumed that convection and migration in an electric are the dominating transport
mechanisms across the boundary, and therefore that the diffusive transport can be
ignored, that is:

n ⋅ ( – D ∇c ) = 0

Note that the Convection or the Migration in electric field transport mechanisms needs
to be included for this node to be available.

Concentration
This condition node adds a boundary condition for the species concentration. For
example, a c = c0 condition specifies the concentration of species c.

CONCENTRATION
Individually specify the concentration for each species. Select the check box for the
Species to specify the concentration, and then enter a value or expression in the
corresponding field. To use another boundary condition for a specific species, click to
clear the check box for the concentration of that species.

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.
You can find details about the different constraint settings in the section Constraint
Reaction Terms in the COMSOL Multiphysics Reference Manual.

Flux
This node can be used to specify the species flux across a boundary. The prescribed flux
of a species c is defined as:

– n ⋅ ( – D∇c ) = J 0

When the mass transport includes migration of ionic species, the flux is defined as:

– n ⋅ ( – D∇c – zu m Fc∇φ ) = J 0

192 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

The flux prescribed, J0, is an arbitrary user-specified flux expression. It can for example
represent a flux due to chemical reactions or phase change, or the transport to or from
a surrounding environment currently not included model. J0 can be constant or a
function of the any dependent variable, for example the concentration, temperature,
pressure or the electric potential φ.

INWARD FLUX
Select the Species check box for the species to specify and enter a value or expression
for the inward flux in the corresponding field. Use a minus sign when specifying a flux
directed out of the system. To use another boundary condition for a specific species,
click to clear the check box for that species.

External convection
Set Flux type to External convection to prescribe a flux to or from an exterior domain
(not modeled) assumed to include convection. The exterior can for example include a
forced convection to control the temperature or to increase the mass transport. In this
case the prescribed mass flux corresponds to

J0 = kc ( cb – c )

where kc is a mass transfer coefficient and cb is the bulk concentration, the typical
concentration far into the surrounding exterior domain.

Symmetry
The Symmetry node can be used to represent boundaries where the species
concentration is symmetric, that is, where there is no mass flux across the boundary.

This boundary condition is identical to that of the No Flux node.

Flux Discontinuity
This node represents a discontinuity in the mass flux across an interior boundary:

– n ⋅ [ ( J + uc ) u – ( J + uc ) d ] = N 0 J = – D∇c – zu m Fc∇φ

where the value N0 (SI unit: mol/(m2·s)) specifies the jump in total flux at the
boundary. This can be used to model a boundary source, for example a surface
reaction, adsorption or desorption.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 193

 FLUX DISCONTINUITY
In this section the jump in species flux (or surface source) is specified.

Select the Species check box for the species to specify and enter a value or expression
for the material flux jump in the corresponding field. To use a different boundary
condition for a specific species, click to clear the check box for the flux discontinuity
of that species.

Partition Condition
The Partition Condition node can be used to prescribe the ratio between the
concentration of a solute species in two different immiscible phases. It can for example
be used on interior boundaries separating two liquid phases, a gas-liquid interface, or
on a boundary separating a liquid phase and a solid or porous media. For a species
concentration ci, the ratio between the concentration on the up side and on the down
side of the boundary (ci,u and ci,d respectively) is defined as

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

in terms of a partition coefficient Ki. The up and down side of the selected boundary
is indicated in the Graphics window. The arrows point from the down side into the up
side.

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

http://www.comsol.com/products/specifications/ for more details on
availability.

PARTITION COEFFICIENT
Select the Reverse direction check box to reverse the direction of the arrows on the
selected boundaries, and the corresponding definition of the up and down side
concentration.

Use the associated input fields to prescribe the partition coefficient Ki.

194 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

FURTHER READING
For an example of using a partition condition, see this application example:

Separation Through Dialysis: Application Library path

Chemical_Reaction_Engineering_Module/Mixing_and_Separation/dialysis

Periodic Condition
The Periodic Condition node can be used to define periodicity for the mass transport
between two sets of boundaries. The node prescribes continuity in the concentration
and the mass flux between the “source” and the “destination” side respectively. Note
that these names are arbitrary and does not influence the direction in which mass is
transported. It is dictated by mass transfer equations in the adjacent domains.

The node can be activated on more than two boundaries, in which case the feature tries
to identify two separate surfaces that each consist of one or several connected
boundaries.

For more complex geometries, it might be necessary to add the Destination Selection
subnode, which is available from the context menu (right-click the parent node) as well
as from the Physics toolbar, Attributes menu. With this subnode, the boundaries that
constitute the source and destination surfaces can be manually specified.

FURTHER READING
For an example of using a periodic condition, see this application example:

The KdV Equation and Solitons: Application Library path

COMSOL_Multiphysics/Equation_Based/kdv_equation

Line Mass Source

The Line Mass Source feature models mass flow originating from a tube or line region
with an infinitely small radius.

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

http://www.comsol.com/products/specifications/ for more details on
availability.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 195

 SELECTION
The Line Mass Source feature is available for all dimensions, but the applicable selection
differs between the dimensions.

MODEL DIMENSION APPLICABLE GEOMETRICAL ENTITY

2D Points
2D Axisymmetry Points not on the symmetry axis and the symmetry axis
3D Edges

SPECIES SOURCE
·
Enter the source strength, q l,c , for each species (SI unit: mol/(m·s)). A positive value
results in species injection from the line into the computational domain, and a negative
value means that the species is removed from the computational domain.

Line sources located on a boundary affect the adjacent computational domains. This
effect makes the physical strength of a line source located in a symmetry plane twice
the given strength.

FURTHER READING
See the section Mass Sources for Species Transport.

Point Mass Source

The Point Mass Source feature models mass flow originating from an infinitely small
domain around a point.

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

http://www.comsol.com/products/specifications/ for more details on
availability.

SPECIES SOURCE
·
Enter the source strength, q p,c , for each species (SI unit: mol/s). A positive value
results in species injection from the point into the computational domain, and a
negative value means that the species is removed from the computational domain.

Point sources located on a boundary or on an edge affect the adjacent computational

domains. This has the effect, for example, that the physical strength of a point source
located in a symmetry plane is twice the given strength.

196 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

FURTHER READING
See the section Mass Sources for Species Transport.

Open Boundary
Use this node to set up mass transport across boundaries where both convective inflow
and outflow can occur. On the parts of the boundary where fluid flows into the
domain, an exterior species concentration is prescribed. On the remaining parts, where
fluid flows out of the domain, a condition equivalent to the Outflow node is instead
prescribed.

The direction of the flow across the boundary is typically calculated by a fluid flow
interface and is provided as a model input to the Transport of Diluted Species
interface.

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

http://www.comsol.com/products/specifications/ for more details on
availability.

EXTERIOR CONCENTRATION
Enter a value or expression for the Exterior concentration.

Thin Diffusion Barrier

Use this boundary condition to model a thin layer through which mass is transported
by diffusion only. The node is applicable on interior boundaries and can be used to
avoid meshing thin structures.

THIN DIFFUSION BARRIER

Specify the Layer thickness, ds, and input a Diffusion coefficient, Ds,c, for each of the
species included.

Thin Impermeable Barrier

This feature models a thin mass transfer barrier. It is available on interior boundaries
and introduces a discontinuity in the concentration across the boundary. On each side,
a no-flux condition is prescribed for the mass transport implying that it acts as a barrier.
The feature can be used to avoid meshing thin structures.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 197

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

If the Apply equilibrium condition on inflow boundaries check box is selected, the
specified inflow concentration values in all active Inflow boundary nodes for the physics
interface are modified to comply with the equilibrium condition.

• A necessary requirement for this is feature to be available is that two or

more species are solved for by the interface.
• This feature is only available in a limited set of add-on products. See
http://www.comsol.com/products/specifications/ for more details
on availability.

EQUILIBRIUM CONDITION
The list defaults to Equilibrium constant or select User defined. For either option, the
Apply equilibrium condition on inflow boundaries check box is selected by default.

For Equilibrium constant, enter an Equilibrium constant Keq (dimensionless). Also enter
a value or expression for the Unit activity concentration Ca0 (SI unit: mol/m3).
Selecting Equilibrium constant defines an equilibrium condition based on the
stoichiometric coefficients, the species activities, and the law of mass action.

For User defined, enter an Equilibrium expression Eeq (dimensionless).

STOICHIOMETRIC COEFFICIENTS
Enter a value for the stoichiometric coefficientνc (dimensionless). The default is 0. Use
negative values for reactants and positive values for products in the modeled reaction.

Species with a stoichiometric coefficient value of 0 are not affected by the Equilibrium
Reaction node.

198 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

FURTHER READING
See

• Equilibrium Reaction Theory

Surface Reactions
The Surface Reactions node can be used to account for the species boundary flux due
to chemical reactions occurring on a surface (heterogeneous reactions). For a domain
species participating in a surface reaction, the boundary flux corresponds to the
reaction rate at the surface.

SURFACE REACTION RATE

Specify the surface reaction rate J0 of each species resulting from the reactions. Note
that if you have the Chemistry interface available, provided with the Chemical
Reaction Engineering Module, the reaction rate expressions can be automatically
generated and picked up using the drop-down menu.

FURTHER READING
For an example of using the Surface Reactions node, see this application example:

Chemical Vapor Deposition of GaAs: Application Library path

Chemical_Reaction_Engineering_Module/
Reactors_with_Mass_and_Heat_Transfer/gaas_cvd

Surface Equilibrium Reaction

Use this node to model an equilibrium reaction on a boundary (surface). The settings
for this node are similar to Equilibrium Reaction. Note that a necessary requirement
for this is feature to be available is that two or more species are solved for by the
interface.

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

http://www.comsol.com/products/specifications/ for more details on
availability.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 199

 Fast Irreversible Surface Reaction
This boundary node defines an irreversible reaction where the kinetics is so fast that
the only factor limiting the reaction rate is the transport of a species to the reacting
surface.

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

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

http://www.comsol.com/products/specifications/ for more details on
availability.

Porous Electrode Coupling

Use this node to add a molar source in a domain that is coupled to one or multiple
Electrode Reaction nodes of an Electrochemistry Interface.

The molar source is calculated from the number of electrons, stoichiometric

coefficients, and volumetric current densities of the coupled porous electrode reactions
specified in the Reaction Coefficients subnodes.

In the Transport of Concentrated Species interface, the molar sources (or sinks) are
multiplied by the species molar masses to obtain the corresponding mass sources.

Additional Reaction Coefficients subnodes are available from the context menu
(right-click the parent node) as well as from the Physics toolbar, Attributes menu.

Note that if you are also modeling the momentum transport and expect a
non-negligible total mass source or sink, which is often the case in gas diffusion
electrodes, you need to also add a corresponding Porous Electrode Coupling node in
the Fluid Flow interface.

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

http://www.comsol.com/products/specifications/ for more details on
availability.

200 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

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
non-negligible total mass flux over the boundary, which is often the case for gas
diffusion electrodes, you need to also add a corresponding Electrode Surface Coupling
node in the Fluid Flow interface.

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

http://www.comsol.com/products/specifications/ for more details on
availability.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 201

 Porous Media Transport Properties
Use this node to model the concentration of diluted species transported through
interstices in porous media. A part form convection and diffusion, the node contains
functionality to include species evolution through adsorption, dispersion, and reaction.

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

http://www.comsol.com/products/specifications/ for more details on
availability.

MODEL INPUTS
The temperature model input is always available. Select the source of the Temperature.
For User defined, enter a value or expression for the temperature in the input field. This
input option is always available.

You can also select the temperature solved for by a Heat Transfer interface added to
the model component. These physics interfaces are available for selection in the
Temperature list.

MATRIX PROPERTIES
Use the Porous material list to define a material specifying the matrix properties on the
current selection. By default the Domain material is used.

Specify the Porosity, εp (dimensionless) of the porous matrix. This is by default taken
From material. Select User defined to instead enter a different value.

CONVECTION
If transport by convection is active, the velocity field of the solvent needs to be
specified. Select the source of the Velocity field. For User defined, enter values or
expressions for the velocity components in the input fields. This input option is always
available.

You can also select the velocity field solved for by a Fluid Flow interface added to the
model component. These physics interfaces are available for selection in the Velocity
field list.

DIFFUSION
Select a Fluid material (when available and applicable).

202 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

Specify the Fluid diffusion coefficient DF,i (SI unit: m2/s). Enter a value or expression
for each of the species in the corresponding input field. The default is 1·10-9 m2/s.

Select the Effective diffusivity model: Millington and Quirk model (the default),
Bruggeman model, Tortuosity model, or User defined. For Tortuosity model, enter a value
for the tortuosity τF,i (dimensionless). The default is 1.

MIGRATION IN ELECTRIC FIELD

This section is available when the Migration in electric field check box is selected. From
the Electric potential list, select the source of the electric field.

• Enter a value or expression for the Electric potential V, which is User defined; this
input option is always available.
• Select the electric potential solved by an AC/DC-based interface that has also been
added to the model.
• Select the electric potential defined or solved by Electrochemistry interface that has
been added to the component.

By default the Mobility is set to be calculated based on the species effective diffusivity
and the temperature using the Nernst-Einstein relation. For User defined, and under
Mobility, select the appropriate scalar or tensor type — Isotropic, Diagonal, Symmetric,
or Anisotropic — and type in the value of expression of the effective mobility ume,c.

Enter the Charge number zc for each species.

DISPERSION
This section is available when the Dispersion in porous media check box is selected on
the Settings window for the physics interface.

Select the Specify dispersion for each species individually check box to specify the
dispersion tensor DD (SI unit: m2/s) for each species separately. The default is to use
the same dispersion tensor DD for all species.

Select an option from the Dispersion tensor list — User defined (the default) or
Dispersivity. For User defined, use it to specify the dispersion components as
user-defined constants or expressions. Select Isotropic, Diagonal, Symmetric, or
Anisotropic based on the properties of the dispersion tensor.

Select Dispersivity when Convection has been added as the transport mechanism. Specify
the dispersivities (SI unit: m) to define the dispersion tensor DD (SI unit: m2/s)
together with the velocity field u. Select an option from the Dispersivity model list:
Isotropic (the default) or Transverse isotropic based on the properties of the porous

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 203

 media. For isotropic porous media, specify the longitudinal and transverse
dispersivities. For transverse isotropic porous media, specify the longitudinal,
horizontal transverse, and vertical transverse dispersivities.

Adsorption
Use this node to model adsorption of the fluid phase species onto the porous media
surface. It is available as a subnode to the Porous Media Transport Properties and the
Partially Saturated Porous Media nodes.

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

http://www.comsol.com/products/specifications/ for more details on
availability.

MATRIX PROPERTIES
Use the Porous material list to define a material specifying the matrix properties on the
current selection. By default the Domain material is used.

The density of the porous media is needed when modeling adsorption to the surface
of the porous matrix. By default Density ρ is defined from the domain material.

ADSORPTION
Select a Sorption type — Langmuir (the default), Freundlich, or User defined to specify
how to compute cP, the amount of species sorbed to the solid phase (moles per unit
dry weight of the solid):

• For Langmuir:

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:

204 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

 c N ∂c P cP
c P = K F  -------- -------- = N -----
- Freundlich
 c ref ∂c c

Enter a Freundlich constant kF,c (SI unit: mol/kg), a Freundlich exponent NF,c
(dimensionless), and a Reference concentration cref,c (SI unit: mol/m3).

• For User defined:

∂c P
cP = KP c -------- = K P User defined
∂c

Enter an Adsorption isotherm kP,c (SI unit: m3/kg).

For more information, see Adsorption in the theory section.

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

Partially Saturated Porous Media

Use this node to model the concentration of diluted species transported by a liquid
through in partially filled porous media. The interstices of the porous media contains
the liquid carrier phase and gas pockets. A part from convection and diffusion, the
node contains functionality to include species evolution through adsorption,
dispersion, reaction, and volatilization.

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

http://www.comsol.com/products/specifications/ for more details on
availability.

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.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 205

 MATRIX PROPERTIES
Use the Porous material list to define a material specifying the matrix properties on the
current selection. By default the Domain material is used.

Specify the Porosity, εp (dimensionless) of the porous matrix. This is by default taken
From material. Select User defined to instead enter a different value.

SATURATION
Select Saturation or Liquid volume fraction from the list.

For Saturation, enter a value for s (dimensionless) between 0 and 1. The liquid volume
fraction is then computed from the saturation and porosity as θ = sεp.

For Liquid volume fraction, enter a value for θ (dimensionless) between 0 and the value
of porosity. The saturation is then computed from the porosity and the liquid volume
fraction as s = θεp.

Select a Fluid fraction time change: Fluid fraction constant in time (the default), Time
change in fluid fraction, or Time change in pressure head.

• For Time change in fluid fraction, enter dθ/dt (SI unit: 1/s).
• For Time change in pressure head, enter dHp/dt (SI unit: m/s) and a Specific
moisture capacity Cm (SI unit: 1/m).

CONVECTION
If transport by convection is active, the velocity field of the solvent needs to be
specified. Select the source of the Velocity field. For User defined, enter values or
expressions for the velocity components in the input fields. This input option is always
available.

You can also select the velocity field solved for by a Fluid Flow interface added to the
model component. These physics interfaces are available for selection in the Velocity
field list.

DIFFUSION
Select a Liquid material from the list.

Specify the Liquid diffusion coefficient DL,c (SI unit: m2/s). Enter a value or expression
for each of the species in the corresponding input field. The default is 1·10-9 m2/s.

Select the Effective diffusivity model, liquid: Millington and Quirk model (the default),
Bruggeman model, Tortuosity model, or User defined. For Tortuosity model, enter a value
for τL,c (dimensionless). The default is 1.

206 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

When the Volatilization in partially saturated porous media check box is selected on the
Settings window for the physics interface, also define the Gas material, Gas diffusion
coefficient, and Effective diffusivity model, gas.

MIGRATION IN ELECTRIC FIELD

This section is available when the Migration in electric field check box is selected. It is
similar to that in Porous Media Transport Properties feature. Select the source of electric
field from the Electric potential list. The default selection to Mobility is the
Nernst-Einstein relation.

DISPERSION
This section is available when the Dispersion in porous media check box is selected on
the Settings window for the physics interface. The settings are the same as for Porous
Media Transport Properties.

VOLATILIZATION
This section is available when the Volatilization in partially saturated porous media check
box is selected on the Settings window for the physics interface.

Enter a value for the Volatilization kG,c (dimensionless) for each species.

Volatilization
This feature is available when the Volatilization in partially saturated porous media check
box is selected on the Settings window for the physics interface.

Use this feature to model mass transfer at the boundary due to volatilization. The
feature can be added on boundaries of a Partially Saturated Porous Media domain. In
this case the porous media contains a liquid phase and a gas phase. The species
dissolved in the liquid are assumed to be vaporized at the boundary, and transported
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 )

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 207

 where hc is the mass transfer coefficient, kG,c the volatilization coefficient, and cGatm,c
the concentration in the surrounding atmosphere.

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

http://www.comsol.com/products/specifications/ for more details on
availability.

VOLATILIZATION
Enter a Mass transfer coefficient hc defining the transfer into the surrounding media.
This can be given by boundary layer theory. When assuming that no convective flow
is present in the surrounding, the mass transfer coefficient can be defined from the gas
diffusion coefficient DGc and the thickness of the diffusion layer ds in the manner of

D Gc
h c = ----------
ds

Also give the atmospheric concentration for each species, cGatm,c. The Volatilization
coefficient kG,c for each species are taken from the adjacent Partially Saturated Porous
Media domain.

Reactive Pellet Bed

Use this feature to model packed bed reactors with catalytic pellets. For details, see the
section Theory for the Reactive Pellet Bed. By default, subnodes for Reactions and are
added.

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

http://www.comsol.com/products/specifications/ for more details on
availability.

BED PARAMETERS
Here you can specify the bed porosity, which is the void fraction in the packed bed
structure. Select From densities to calculate the porosity from the bed density and the
individual pellet density. Select User defined to specify the porosity directly.

PELLET SHAPE AND SIZE

The default shape is spherical. Cylinders, flakes, and user-defined shapes can also be
selected. A uniform pellet size or a discrete size distribution can be selected. Select a

208 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

Pellet size distribution — Uniform size (the default), Two sizes, Three sizes, Four sizes, or
Five sizes to select up to five different particle sizes.

Depending on the shape selection, equivalent radii or volumes and surface areas will
be required as input. If a size distribution is selected, the volume percentage of each
size is required as input.

Note that different chemical reactions can be specified for each pellet size if a
distribution is specified.

SURFACE SPECIES
In order to add surface species, click the Add button and enter the species name in the
Surface species table. Added surface species are be available inside all pellet types
defined in the Pellet Shape and Size section, but not in the bulk fluid.

For each pellet type, specify the Reactive specific surface area, Sb,reac (SI unit: 1/m),
corresponding to the surface area, per volume, available for surface reactions.

PELLET PARAMETERS
Enter a Pellet porosity εpe (dimensionless) to specify the porosity of the pellet internals.

Select Diffusion model — Millington and Quirk model (the default), Bruggeman model,
Tortuosity model, or User defined to describe the effective correction of the diffusion
coefficient in the pellet. In the case of the Tortuosity model, a value for the tortuosity
τpe within the pellet is required.
Enter also the Diffusion coefficient Dpe,c (SI unit: m2/s). If a User defined diffusion
model is selected, an Effective diffusion coefficient Dpeff,c (SI unit: m2/s) is entered. The
default value is 1·10-9 m2/s in both cases.

PELLET-FLUID SURFACE
For the coupling of concentration between the pellet internals and the surrounding
fluid, two Coupling type options are available:

• Continuous concentration, assuming that all resistance to mass transfer to/from the
pellet is within the pellet and no resistance to pellet-fluid mass transfer is on the bulk
fluid side. The concentration in the fluid will thus be equal to that in the pellet pore
just at the pellet surface: c pe,i = c i . This constraint also automatically ensures flux
continuity between the internal pellet domain and the free fluid domain through
so-called reaction forces in the finite element formulation.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 209

 • Film resistance (mass flux): The flux of mass across the pellet-fluid interface into the
pellet is possibly rate determined on the bulk fluid side, by film resistance. The
resistance is expressed in terms of a film mass transfer coefficient, hDi, such that:
N i,inward = h D, i ( c i – c pe, i ) .

The Film resistance (mass flux) option computes the inward surface flux,
Ni,inward=hDi(ci-cpe,i). hDi is the mass transfer coefficient (SI unit: m/s) and is
calculated with the default Automatic setting from a dimensionless Sherwood number
expression or with User defined mass transfer coefficients.

The Active specific surface area (SI unit: m-1) is required to couple the mass transfer
between the pellets and the bed fluid. Select either the Automatic setting that calculates
the specific surface area from the shape information given above. User defined is also
available for explicit surface area specification.

The Sherwood number expression can be computed from three available expressions:
Frössling, Rosner, and Garner and Keey. The Frössling equation is the default and
probably the most commonly used for packed spheres. All of these are based on the
dimensionless Reynolds, Re, and Schmidt, Sc, numbers, which are computed from
Density and Dynamic viscosity. Select these to be taken either From material or choose
the User defined alternative.

PELLET DISCRETIZATION
The extra dimension in the pellet needs to be discretized into elements. Select a
Distribution — Cubic root sequence (the default), Linear, or Square root sequence. Enter
the Number of elements Nelem.

CONSTRAINT SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.
See the details about the different constraint settings in the section Constraint
Reaction Terms in the COMSOL Multiphysics Reference Manual.

FURTHER READING
Theory for the Reactive Pellet Bed in the Theory section of this manual.

210 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

For an application using the Reactive Pellet Bed feature, see

• A Multiscale 3D Packed Bed Reactor: Application Library path

Chemical_Reaction_Engineering_Module/Reactors_with_Porous_Catalysts/
packed_bed_reactor_3d
Web link: http://www.comsol.com/model/
a-multiscale-3d-packed-bed-reactor-17019

Reactions
The Reactions subfeature to the Reactive Pellet Bed is used to define reaction terms to
the transport within the reactive pellets. The feature also defines the corresponding
averaged heat sources to be applied to heat transport in the bulk fluid.

DOMAIN SELECTION
From the Selection list, choose the domains on which to define rate expression or
expressions that govern source terms in the transport equations.

Several reaction nodes can be used to account for different reactions in different parts
for the modeling geometry.

REACTION RATES
Add a rate expression R (SI unit: mol/(m3·s)) for species i using a value or an
expression. One reaction rate per species and pellet type can be entered.

Note that if you have the Chemistry interface available, provided with the Chemical
Reaction Engineering Module, the reaction rate expressions can be automatically
generated and picked up using the drop-down menu. For an example, see the
application Fine Chemical Production in a Plate Reactor.

SURFACE REACTION RATES

The section is available when one or more surface species have been added in the
Surface Species section of the Reactive Pellet Bed feature.

Specify the rate expression R (SI unit: mol/(m2·s)) corresponding to the surface
reaction rate of each volumetric species i participating in the surface reaction.
Furthermore, specify the surface reaction rates for the participating surface species in
the corresponding table.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 211

 If several pellet types have been defined, one set of surface reaction rates per pellet type
can be defined.

Note that if you have the Chemistry interface available, provided with the Chemical
Reaction Engineering Module, the reaction rate expressions can be automatically
generated and picked up using the drop-down menu.

HEAT SOURCE
Specify the heat source originating from the heat of reaction of the chemical reactions
inside the pellet can be specified. Both heat sources from reactions in the fluid, and
heat sources resulting from surface reactions can be defined. When using several pellet
types, heat sources for each type can be added.

The heat sources are most conveniently picked up from a Chemistry feature that
defines the reaction rate and the heat of reactions. In that case, the Rate expression can
be selected from the drop-down menu. Else it can be set to User Defined.

The defined heat source can be used by a Heat Source feature in any of the heat
transfer interfaces.

Species Source
In order to account for consumption or production of species in porous domains, the
Species Source node adds source terms expressions Si to the right-hand side of the
species transport equations.

DOMAIN SELECTION
From the Selection list, choose the domains on which to define rate expression or
expressions that govern the source term in the transport equations.

If there are several types of domains, with subsequent and different reactions occurring
within them, it might be necessary to remove some domains from the selection. These
are then defined in an additional Species Source node.

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.

212 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

Hygroscopic Swelling
The Hygroscopic Swelling multiphysics coupling node ( ) is used for moisture
concentration coupling between the Solid Mechanics interface and either the
Transport of Diluted Species or Transport of Diluted Species in Porous Media
interfaces.

Hygroscopic swelling is an effect of internal strain caused by changes in moisture

content. This strain can be written as

ε hs = β h M m ( c mo – c mo,ref )

where βh is the coefficient of hygroscopic swelling, Mm is the molar mass, cmo is the
moisture concentration, and cmo,ref is the strain-free reference concentration.

It requires a license of either the MEMS Module or the Structural Mechanics Module.
The multiphysics feature will appear automatically if both the Transport of Diluted
Species and the Solid Mechanics interfaces are added to the same component. For the
most current information about licensing, please see See http://www.comsol.com/
products/specifications/.

FURTHER READING
More information about how to use hygroscopic swelling can be found in Hygroscopic
Swelling Coupling section in the Structural Mechanics Module User’s Guide.

More information about multiphysics coupling nodes can be found in the section The
Multiphysics Branch in the COMSOL Multiphysics Reference Manual.

Fracture
Use this node to model mass transport along thin fractures in porous media. The node
assumes that the transport in the tangential direction along the fracture is dominant,
as a result of lower flow resistance.

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

http://www.comsol.com/products/specifications/ for more details on
availability.

FRACTURE PROPERTIES
Specify a value for the Fracture thickness dfr.

THE TRANSPORT OF DILUTED SPECIES INTERFACE | 213

 MATRIX PROPERTIES
Use the Porous material list to define a material specifying the matrix properties on the
current selection. By default the Boundary material is used.

Specify the Porosity, εp (dimensionless) of the porous matrix. This is by default taken
From material. Select User defined to instead enter a different value.

CONVECTION
Select an option from the Velocity field list to specify the convective velocity along the
fracture. For a consistent model, use a Fracture Flow feature in a Darcy’s Law interface
to compute the fluid flow velocity in the fracture.

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

The settings for the Diffusion, and Dispersion sections are the same as for
Porous Media Transport Properties.

214 | CHAPTER 3: 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
http://www.comsol.com/products/specifications/

SETTINGS
The Label is the default physics interface name.

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

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

BOUNDARY SELECTION
If model geometry includes boundaries that should not be included in the mass
transfer simulation, remove those from the selection list.

TRANSPORT MECHANISMS
Mass transport due to diffusion is always included. Use the Convection check box,
available under Additional transport mechanisms, to control whether to also include
convective transport.

THE TRANSPORT OF DILUTED SPECIES IN FRACTURES INTERFACE | 215

 CONSISTENT STABILIZATION
To display this sections, click the Show button ( ) and select Stabilization. Use this
section to control the application of the available consistent stabilization methods;
Streamline diffusion and Crosswind diffusion.

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

INCONSISTENT STABILIZATION
To display this section, click the Show button ( ) and select Stabilization. By default,
the Isotropic diffusion check box is not selected, because this type of stabilization adds
artificial diffusion and affects the accuracy of the original problem. However, this
option can be used to get a good initial guess for underresolved problems.

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

The Value type when using splitting of complex variables setting should in most pure
mass transfer problems be set to Real, which is the default. It makes sure that the
dependent variable does not get affected by small imaginary contributions, which can
occur, for example, when combining a Time Dependent or Stationary study with a
frequency-domain study. For more information, see Splitting Complex-Valued
Variables in the COMSOL Multiphysics Reference Manual.

216 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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

Boundary, Edge, Point, and Pair Nodes for the Transport of Diluted
Species in Fractures Interface
The Transport of Diluted Species Interface has the following boundary, edge, point,
and pair nodes, listed in alphabetical order, available from the Physics ribbon toolbar
(Windows users), Physics context menu (Mac or Linux users), or by right-clicking to
access the context menu (all users).

• Adsorption • No Flux
• Concentration • Outflow
• Flux • Reactions
• Fracture • Species Source
• Inflow
• Initial Values

THE TRANSPORT OF DILUTED SPECIES IN FRACTURES INTERFACE | 217

 Adsorption
Use this node to model adsorption of the fluid phase species in onto the porous media
surface of the fracture.

MATRIX PROPERTIES
Use the Porous material list to define a material specifying the matrix properties on the
current selection. By default the Domain material is used. The density of the porous
media is needed when modeling adsorption to the surface of the porous matrix. By
default Density ρ is set to from domain material.

adsorption

Select a Sorption type—Langmuir (the default), Freundlich, or User defined to specify

how to compute cP, the amount of species sorbed to the solid phase (moles per unit
dry weight of the solid):

• For Langmuir:

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

Enter a Langmuir constant kL,c (SI unit: m3/mol) and an Adsorption maximum
cp,max,c (SI unit: mol/kg):

• For Freundlich:

c N ∂c P cP
c P = K F  -------- -------- = N -----
- Freundlich
 c ref ∂c c

Enter a Freundlich constant kF,c (SI unit: mol/kg), a Freundlich exponent NF,c
(dimensionless), and a Reference concentration cref,c (SI unit: mol/m3).

• For User defined:

∂c P ∂
cP = KP c -------- = ( K P c ) User defined
∂c ∂c

Enter an Adsorption isotherm kP,c (SI unit: m3/kg).

For more information, see Adsorption in the theory section.

218 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

Flux
This node can be used to specify the species flux across a boundary of a porous fracture
(applied in points in 2D and along edges in 3D). The flux of species c is defined as

n ⋅ ( D e ∇c ) = N 0

where N0 is an arbitrary user-specified flux expression. For example, N0 can represent

a flux due to chemical reactions, or a phase change. A positive N0 implies that the
concentration inside the fracture increases.

INWARD FLUX
Specify the flux of each species individually. To use another boundary condition for a
specific species, click to clear the check box for the mass fraction of that species.

Fracture
Use this node to model mass transport along thin fracture surfaces situated inside
porous or solid material. The node assumes that the transport in the tangential

THE TRANSPORT OF DILUTED SPECIES IN FRACTURES INTERFACE | 219

 direction of the fracture is dominant, as a result of lower flow resistance. Note that the
fracture it self is modeled as porous.

MATRIX PROPERTIES
Use the Porous material list to define a material specifying the matrix properties on the
current selection. By default the Boundary material is used.

Specify the Porosity, εp (dimensionless) of the porous matrix. This is by default taken
From material. Select User defined to instead enter a different value.

CONVECTION
Select an option from the Velocity field list to specify the convective velocity along the
fracture. For a consistent model, use The Fracture Flow Interface to compute the fluid
flow velocity.

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

The settings for the Diffusion, and Dispersion sections are the same as for Porous Media
Transport Properties.

Inflow
Use this node to specify all species concentrations at a fracture inlet. The condition is
applied in points in 2D and along edges in 3D

If you want to specify the concentration of a subset of the partaking species, this can
be done by using the Concentration node instead.

CONCENTRATION
For the concentration of each species c0,c (SI unit: mol/m3), enter a value or
expression.

BOUNDARY CONDITION TYPE

This section in the settings is only available for some products. Search for “Inflow” on
the page: http://www.comsol.com/products/specifications/ for more details on
availability.

The option Concentration constraint constrains the concentration values on the

boundary by the use of pointwise constraints. The other option, Flux (Danckwerts) can
be more stable and fast to solve when high reaction rates are anticipated in the vicinity
of the inlet. Oscillations on the solutions can also be avoided in such cases. The latter

220 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

BOUNDARY SELECTION
From the Selection list, choose the boundaries on which to define rate expression or
expressions that govern the source term in the transport equations.

Several reaction nodes can be used to account for different reactions in different parts
of the fracture.

REACTION RATES
Add a rate expression Ri for species i. Enter a value or expression in the field. Note that
if you have the Chemistry interface available, provided with the Chemical Reaction

THE TRANSPORT OF DILUTED SPECIES IN FRACTURES INTERFACE | 221

 Engineering Module, the reaction rate expressions can be automatically generated and
picked up using the drop-down menu.

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.

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.

222 | CHAPTER 3: 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 http://www.comsol.com/products/specifications/).

Some examples of what can be studied with this physics interface include:

• The evolution of 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 | 223

 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 an individual species i is:

∂ ρω
( i ) + ∇ ⋅ ( ρω i u ) = – ∇ ⋅ j i + R i (3-100)
∂t

The displayed formulation changes depending on the active transport mechanisms and
the selected diffusion model.

TRANSPORT MECHANISMS
The Transport of Concentrated Species interface always accounts for transport due to
diffusion.

The available diffusion models and the additional transport mechanisms differs
between various COMSOL products (see http://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

224 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

 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. The Convection check box is selected by default. The second
term on the left-hand side of Equation 3-100 represents mass transport by convection.

Migration in Electric Field

Select the Migration in electric field check box to activate migration of ionic species due
to an electric field. The resulting migration term is part of the relative mass flux vector.

Mass Transport in Porous Media

The Mass transport in porous media check box activates functionality specific to species
transport in porous media. When selected the following features are enabled:

• Porous Media Transport Properties

• Porous Electrode Coupling

Knudsen Diffusion
For Mixture-averaged and Fick’s law, it is possible to include Knudsen diffusion. This
mechanism accounts for species collisions with the surrounding media, for example,
the pore walls the species pass through. It is also an important component when setting
up a Dusty gas model.

Maxwell-Stefan Diffusion Model

When using the Maxwell-Stefan diffusion model the relative mass flux vector is

Q T
Di
j i = – 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 (3-101)
l=1

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 225

 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 (3-102)
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.

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 3-103 (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 (3-103)
i=2

226 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

CONSISTENT AND INCONSISTENT STABILIZATION
To display this section, click the Show button ( ) and select Stabilization.

• There are two consistent stabilization methods available when using the
Mixture-Averaged Diffusion Model or Fick’s Law Diffusion Model—Streamline
diffusion and Crosswind diffusion. Both are active by default.
The Residual setting applies to both the consistent stabilization methods.
Approximate residual is the default setting and it means that derivatives of the
diffusion tensor components are neglected. This setting is usually accurate enough
and computationally faster. If required, select Full residual instead.
• There is one inconsistent stabilization method, Isotropic diffusion, which is available
when using the Mixture-Averaged Diffusion Model or Fick’s Law Diffusion Model.

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

Regularization
From the Regularization list, select On (the default) or Off. When turned On, regularized
mass fractions are calculated such that

0 ≤ w i, reg ≤ 1

Regularized mass fractions are used for the calculation of composition-dependent

material properties, such as the density.

Diffusion
The Diffusion settings are available for the approximate diffusion models
Mixture-averaged and Fick’s law.

When the Mixture diffusion correction is enabled, a flux correction is added to ensure
that the net diffusive flux is zero. This typically also mean that the solution becomes
less sensitive to the species selected to be computed from the mass constraint in the
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.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 227

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

• Domain, 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 Batteries_and_Fuel_Cells_Module/Fuel_Cells/
pem_gdl_species_transport_2d
Web link: http://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,

228 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

Adding a Chemical Species Transport Interface and Specifying the

Number of Species

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

For axisymmetric components, COMSOL Multiphysics takes the axial

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

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 229

 These nodes are described in this section or as indicated:

• Electrode Surface Coupling • Porous Media Transport Properties

• Equilibrium Reaction • Reaction
• Flux • Reaction Sources
• Flux Discontinuity • Surface Equilibrium Reaction
• Inflow • Symmetry
• Initial Values • Thin Impermeable Barrier1
• Mass Fraction • Turbulent MixingTransport
• No Flux Properties

• Open Boundary
• Outflow

Some features require certain add-on modules. See details http://

www.comsol.com/products/specifications/
1 The node is described for the Transport of Diluted Species interface.

Transport Properties
The Transport Properties is the main node used to model mass transfer in a fluid
mixture with the Transport of Concentrates species interface. The node adds the
equations governing the mass fractions of all present species, and provides inputs for
the transport mechanisms and for the material properties of the fluid mixture.

The settings in this node are dependent on the check boxes selected under Transport
Mechanisms in the Settings window of the Transport of Concentrated Species
interface.

When the Convection check box is selected, the Turbulent Mixing subnode is available
from the context menu as well as from the Physics toolbar, Attributes menu.

The options available in this feature differs between COMSOL products. (See http:/
/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,

230 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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 3-101 (that is, when a Maxwell-Stefan Diffusion Model is used) and when
calculating the density from the ideal gas law.

Temperature
Select the source of the Temperature field T:

• Select User defined to enter a value or an expression for the temperature (SI unit: K).
This input is always available.
• If required, select a temperature defined by a Heat Transfer interface present in the
model (if any). For example, select Temperature (ht) to use the temperature defined
by the Heat Transfer in Fluids interface with the ht name.

Absolute Pressure
Select the source of the Absolute pressure p:

• Select User defined to enter a value or an expression for the absolute pressure
(SI unit: Pa). This input is always available.
• In addition, select a pressure defined by a Fluid Flow interface present in the model
(if any). For example, select Absolute pressure (spf) to use the pressure defined in a
Laminar Flow interface with spf as the Name.

DENSITY
Define the density of the mixture and the molar masses of the participating species.

Mixture Density
Select a way to define the density from the Mixture density list — Ideal gas or User
defined:

• For Ideal gas, the density is computed from the ideal gas law in the manner of:
pM
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.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 231

 Molar Mass
Enter a value or expression for the Molar mass Mw for each species. The default value
is 0.032 kg/mol, which is the molar mass of O2 gas.

CONVECTION
This section is available when the Convection check box is selected.

Select the source of the Velocity field u:

• Select User defined to enter manually defined values or expressions for the velocity
components. This input is always available.
• Select a velocity field defined by a Fluid Flow interface present in the model (if any).
For example, select Velocity field (spf) to use the velocity field defined by the Fluid
Properties node fp1 in a Single-Phase Flow, Laminar Flow interface with spf as the
Name.

DIFFUSION
Specify the molecular and thermal diffusivities of the present species based on the
selected Diffusion model.

When using a Maxwell-Stefan Diffusion Model or a Mixture-Averaged Diffusion

Model, select the Binary diffusion input type (Table or Matrix) and specify the
Maxwell-Stefan diffusivities in the table or matrix, then enter the Thermal diffusion
T
coefficients D w .
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 inter-diffusion 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.

232 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

Diffusion Coefficient
Using a Fick’s Law Diffusion Model, the diffusion is by default assumed to be isotropic
F
and governed by one Diffusion coefficient D w (SI unit: m2/s) for each species. To allow
for a general representation, it is also possible to use diffusion matrices (diagonal,
symmetric, or anisotropic).

Thermal Diffusion Coefficient

T
To model thermal diffusion, prescribe the Thermal diffusion coefficients D i
(SI unit: kg/(m·s)), by entering one thermal diffusion coefficient for each species in
the corresponding field. In a multicomponent mixture, the sum of the thermal
diffusion coefficients is zero. The default value for all thermal diffusion coefficients
is 0.

Specify the molecular and thermal diffusivities of the present species based on the
selected Diffusion model.

KNUDSEN DIFFUSION
The Knudsen diffusion transport mechanism accounts for the interaction of the species
with the surroundings (interspecies collisions excluded) — for example, the pore wall
when a species passes through porous media.

Depending on which Diffusion model is selected, either the Fick’s law or the
M
Mixture-averaged diffusion coefficient D i is corrected with the Knudsen diffusion
K
coefficient D i in the following way

MK  1 1 -
-1
Di =  --------
- + ------- 
 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.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 233

 Electric Potential
• Select User defined to enter a value or expression for the electric potential . This input
is always available.
• If required, select an electric potential defined by an AC/DC interface that is
present in the model (if any). For example, select Electric potential (ec) to use the
electric field defined by the Current Conservation node cucn1 in an Electric
Currents interface ec.

Settings for the mobilities are used for the Mixture-averaged and Fick’s law transport
models. By default the mobility is set to be calculated based on the species diffusivities
and the temperature using the Nernst-Einstein relation. To manually specify the
mobilities, select User defined for the mobility um,c (SI unit: s·mol/kg) and enter one
value for each species.

Enter the Charge number zc (dimensionless, but requires a plus or minus sign) for each
species.

The temperature (if you are using mobilities based on the Nernst-Einstein relation) is
taken from the Model Inputs section.

Porous Media Transport Properties

The Porous Media Transport Properties node is used to model mass transfer in porous
media using the Transport of Concentrated Species interface. The node adds the
equations governing the mass fractions of all present species, and provides inputs for
the transport mechanisms and for the material properties of the fluid mixture.

The settings in this node are dependent on the check boxes selected under Transport
Mechanisms in the Settings window of the Transport of Concentrated Species
interface.

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

http://www.comsol.com/products/specifications/ for more details on
availability.

MODEL INPUTS
Specify the temperature and pressure to be used in the physics interface. The
temperature model input is used when calculating the density from the ideal gas law,
but also when thermal diffusion is accounted for by supplying thermal diffusion
coefficients. The pressure model input is used in the diffusional driving force in

234 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

Equation 3-101 (that is, when a Maxwell-Stefan Diffusion Model is used) and when
calculating the density from the ideal gas law.

Temperature
Select the source of the Temperature field T:

• Select User defined to enter a value or an expression for the temperature (SI unit: K).
This input is always available.
• If required, select a temperature defined by a Heat Transfer interface present in the
model (if any). For example, select Temperature (ht) to use the temperature defined
by the Heat Transfer in Fluids interface with the ht name.

Absolute Pressure
Select the source of the Absolute pressure p:

• Select User defined to enter a value or an expression for the absolute pressure
(SI unit: Pa). This input is always available.
• In addition, select a pressure defined by a Fluid Flow interface present in the model
(if any). For example, select Absolute pressure (spf) to use the pressure defined in a
Laminar Flow interface with spf as the Name.

MATRIX PROPERTIES
Enter a value or expression for the Porosity, εp (dimensionless), of the porous media.

In order use a porosity defined in a material; specify the material using the Porous
material list, and select From material from the Porosity list.

DENSITY
Use this section to define the mixture density, 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:

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 235

 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.

Molar Mass
Enter a value or expression for the Molar mass Mw for each species. The default value
is 0.032 kg/mol, which is the molar mass of O2 gas.

CONVECTION
This section is available when the Convection check box is selected.

Select the source of the Velocity field u:

• Select User defined to enter values or expressions for the velocity components. This
input is always available.
• Select a velocity field defined by a Fluid Flow interface present in the model (if any).
For example, select Velocity field (spf) to use the velocity field defined by the Fluid
Properties node fp1 in a Single-Phase Flow, Laminar Flow interface with spf as the
Name.

DIFFUSION
Specify the species molecular and thermal diffusivities in nonporous media in the
manner described for the Transport Properties node.

To account for the effect of porosity in the diffusivities, select an Effective diffusivity
model — Millington and Quirk model, Bruggeman model, Tortuosity model, or No
correction. Using one of the first four models, the effective transport factor, fe, is
defined from the porosity and the fluid tortuosity factor in the manner of:

εp
f e = ----- (3-104)
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 τ F .

236 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

The species diffusivities and mobilities are automatically adjusted for porous media
transport using the effective transport factor.

MIGRATION IN ELECTRIC FIELD

This section is available when the Migration in electric field check box is selected in the
Transport Mechanisms section of the interface, select the source of the Electric
potential V:

• Select User defined to enter a value or expression for the electric potential. This input
is always available.
• If required, select an electric potential defined by an AC/DC interface that is
present in the model (if any). For example, select Electric potential (ec) to use the
electric field defined by the Current Conservation node cucn1 in an Electric
Currents interface ec.

Settings for the mobilities are needed for the Mixture-averaged and Fick’s law diffusion
models. By default the mobility is set to be calculated based on the species diffusivities
(adjusted by the Effective diffusivity model in the Diffusion section) using the
Nernst-Einstein relation. To manually specify the mobilities, select User defined for the
mobility um,w (SI unit: s·mol/kg) and enter one value for each species.

Enter the Charge number zc (dimensionless, but requires a plus or minus sign) for each
species.

The temperature (if you are using mobilities based or the Nernst-Einstein relation) is
taken from the Model Inputs section.

Electrode Surface Coupling

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

http://www.comsol.com/products/specifications/ for more details on
availability.

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 237

 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 The Stefan Velocity.

Select Account for Stefan velocity to update the Stefan velocity in accordance with the
mass flux from the electrode reactions. One example that may benefit from this is when
modeling gas diffusion electrodes.

Turbulent Mixing
Use this node to account for the species mixing caused by turbulent flow, typically
when the specified velocity field corresponds to a RANS solution. The node defines
the turbulent mass diffusion from the turbulent kinematic viscosity and a turbulent
Schmidt number.

This node is available if Convection is selected as a transport mechanism and if the

Diffusion model is Mixture-averaged or Fick’s law.

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

http://www.comsol.com/products/specifications/ for more details on
availability.

The Turbulent Mixing feature should not be used together with the
Reacting Flow coupling feature. In this case the turbulent mixing is added
by the coupling feature.

The Turbulent Mixing subnode is available from the context menu (right-click the
Transport Properties parent node) or from the Physics toolbar, Attributes menu.

TURBULENT MIXING
Physics interfaces capable of solving for turbulent fluid flow provide the turbulent
kinematic viscosity, and these appear as options in the Turbulent kinematic viscosity νT
(SI unit: m2/s) list. The list always contains the User defined option that makes it
possible to enter any value or expression.

The default Turbulent Schmidt number ScT is 0.71 (dimensionless).

238 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

Reaction
Use the Reaction node to define species source terms resulting from a single chemical
reaction.

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 http:/
/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

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 239

 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.

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 ω i ≤ 0 for a reactant species, the reaction rate contribution to that species is
completely removed. Similarly, the if the mass fraction for a product species ωj becomes
larger than 1−ωjdl, the rate expression added to that species is damped linearly. If
ω j ≥ 1 for a product species, the reaction rate contribution to that species is
completely removed.

The default value for the damping limit, ωidl, is 1e−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
In order to account for consumption or production of species due to one or more
reactions, the Reaction Sources node adds source terms to the right-hand side of the
species transport equations.

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.

240 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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 ( ω 0, ω1 for example)

• Mole fractions to enter mole fractions ( x 0, ω1 for example)
• Molar concentrations (SI unit: mol/m3) to enter molar concentrations ( c 0, ω1 for
example)
• Number densities (SI unit: 1/m3) to enter number densities ( n 0, ω1 for example)
• Densities (SI unit: kg/m3) to enter densities ( ρ 0, 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

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 241

 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.

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 non-negligible mass flux can be
consistently handled by accounting for the 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 across a boundary. The boundary mass flux for each species is defined in the
manner of:

– n ⋅ j i = j 0, i (3-105)

242 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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, and be a function of ωi, temperature, pressure or even electric potential.

INWARD FLUX
Specify the Inward flux for each species individually. Select the check box for the species
to prescribe a flux and enter a value or expression for the flux 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

j 0, i = k ω, i ( ω b, i – ω i ) (3-106)

where k ω, i is a mass transfer coefficient and ωb,i is the bulk mass fraction, the typical
mass fraction far into the surrounding exterior domain.

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 The Stefan Velocity.

Select Account for Stefan velocity to update the Stefan velocity in accordance with the
prescribed flux. Examples of cases that may benefit from this are for example when
modeling surface reactions or phase change on an exterior boundary.

Inflow
The Inflow node adds a boundary condition for an inflow boundary where one
condition for each species is specified. It is available for exterior boundaries. The
condition can be specified using the following quantities:

• The mass fraction: ω = ω0

• The mole fraction: x = x0
• The molar concentration: c = c0

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 243

 • The number density, which describes the number of particles per volume: n = n0
• The density: ρ = ρ0

A concentration quantity other than the mass fractions can only be used when all
species are defined, as in this boundary condition. The other quantities are
composition dependent and therefore unambiguous only when all species are defined.
For this reason the Mass Fraction node, which allows some species to use a different
boundary condition, only includes inputs for the mass fractions.

INFLOW
Select a Mixture specification:

• Mass fractions (the default) to enter mass fractions ( ω 0, ω1 for example)

• Mole fractions to enter mole fractions ( x 0, ω1 for example)
• Molar concentrations (SI unit: mol/m3) to enter molar concentrations ( c 0, ω1 for
example)
• Number densities (SI unit: 1/m3) to enter number densities ( n 0, ω1 for example)
• Densities (SI unit: kg/m3) to enter densities ( ρ 0, 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.

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

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

244 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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 Maxwell-Stefan Diffusion Model:

– n ⋅ ρω i  Dik dk = 0
k

• 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.

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

THE TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 245

 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)
• 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

246 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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

http://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.

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 TRANSPORT OF CONCENTRATED SPECIES INTERFACE | 247

 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

http://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 non-negligible mass flux can be
consistently handled by accounting for the 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.

248 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

The Nernst-Planck Equations
Interface
Ionic solutions subjected to electric fields are affected by migration transport in
addition to the existing mass transport by diffusion and convection. Migration implies
that positive ions migrate from positive to negative potential, and vice versa for
negatively charged ions. The flux of the ionic species i in the solution is given by the
mass flux vector (SI unit: mol/(m2·s))

N i = – D i ∇c i – z i u m, i Fc i ∇V + c i u (3-107)

where ci denotes the concentration of species i (SI unit: mol/ m3), Di is the diffusion
coefficient of species i (SI unit: m2/s), u is the solvent velocity (SI unit: m/s), F refers
to Faraday’s constant (SI unit: s·A/mol), V denotes the electric potential (SI unit: V),
zi is the charge number of the ionic species (dimensionless), and um,i its ionic mobility
(SI unit: s·mol/kg).

There are three physics interfaces for this type of transport. In the Nernst-Planck
Equations (npe) interface ( ), found under the Chemical Species Transport
branch ( ) when adding a physics interface, the transport of every charged species is
accounted for, and is solved for in combination with the electroneutrality condition.

The Nernst-Planck Equations interface supports modeling of transport by convection,

diffusion, and migration of dissolved ionic species in 1D, 2D, and 3D as well as for
axisymmetric models in 1D and 2D. The dependent variables are the species
concentrations, ci, and the electric potential, V. The physics interface is tailored for
modeling of electrochemical cells and corrosion processes and offers a straightforward
way to perform tertiary current distribution analysis.

The physics interface has the equations, boundary conditions, and rate expression
terms for modeling mass transport of ionic species by convection, diffusion, and
migration, solving for the species concentrations and the electric potential. The main
feature is the Convection, Diffusion, and Migration node, which adds the equation for
the species concentration and the potential and provides an interface for defining
species properties and model inputs.

When this physics interface is added, these default physics nodes are also added to the
Model Builder—Convection, Diffusion and Migration, No Flux (the default boundary
condition for species concentrations), Electric Insulation (the default boundary

THE NERNST-PLANCK EQUATIONS INTERFACE | 249

 condition for the electric field), and Initial Values. Then, from the Physics toolbar, add
other nodes that implement, for example, boundary conditions and rate expression
terms. You can also right-click Nernst-Planck Equations 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 npe.

SPECIES
Select the species that the physics interface computes from the electroneutrality
condition in Equation 3-107. That is, its value comes from the fact that the net charge
in every control volume is zero. Select the preferred species in the From
electroneutrality list. To minimize the impact of any numerical errors, use the species
with the highest concentration. By default, the software uses the first species.

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 species button ( ). To remove a species, select it in the list and
click the Remove species button ( ).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 model.

250 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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.

Convective Term Formulation

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.

CONSISTENT AND INCONSISTENT STABILIZATION

To display this section, click the Show button ( ) and select Stabilization. Any settings
unique to this physics interface are listed below.

The crosswind diffusion implementation used in the Nernst-Planck Equations

interface is based on Codina (Ref. 1).

• When the Crosswind diffusion check box is selected, the Lower gradient limit glim
(SI unit: mol/m4) field defaults to 0.1[mol/m^3)/npe.helem, where npe.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.

• Domain and Boundary Nodes for the Nernst-Planck Equations

Interface
• Theory for the Nernst-Planck Equations Interface
• Convective Term Formulation

THE NERNST-PLANCK EQUATIONS INTERFACE | 251

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

Domain and Boundary Nodes for the Nernst-Planck Equations

Interface
The Nernst-Planck Equations Interface has these domain and boundary physics nodes
available.

DOMAIN NODES
• Convection, Diffusion, and Migration
• Reactions
• Equilibrium Reaction is described for the Transport of Diluted Species interface
• Initial Values

BOUNDARY CONDITIONS

In the Nernst-Planck Equations interface, there are separate boundary

conditions for the species concentrations and for the electric potential.
This means that there are two active boundary conditions on each
boundary. Many different combinations of boundary conditions can be
set for the electric field and concentration fields on a boundary, but not
all combinations are relevant.

SPECIES CONCENTRATION BOUNDARY CONDITIONS

The following boundary conditions for the species concentrations are available on
exterior boundaries:

• Concentration • Symmetry
• Flux • Inflow
• No Flux (the default boundary • Outflow
condition for species concentrations)

252 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

For interior boundaries, continuity in the concentration of all species is the default
boundary condition. In addition, the Flux Discontinuity boundary condition is
available on interior boundaries.

ELECTRIC POTENTIAL BOUNDARY CONDITIONS

The following boundary conditions for the electric potential are available on exterior
boundaries:

• Current Density
• Electric Insulation (the default boundary condition for the electric potential)
• Electric Potential (described for the Electrostatics interface in the COMSOL
Multiphysics Reference Manual)

For interior boundaries, continuity in the electric potential is the default boundary
condition. In addition, the following boundary conditions are available on interior
boundaries:

• Current Discontinuity
• Electric Potential (described for the Electrostatics interface in the COMSOL
Multiphysics Reference Manual)

EDGES AND POINTS

The Point Mass Source and Line Mass Source features are also available and described
for the Transport of Diluted Species interface.

The links to the physics nodes described in the COMSOL Multiphysics

Reference Manual do not work in the PDF, only from the online help.

For axisymmetric models, 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.

Convection, Diffusion, and Migration

The Convection, Diffusion, and Migration is the main physics interface node which adds
the concentration and electric field variables and the Nernst-Planck equations
governing them.

THE NERNST-PLANCK EQUATIONS INTERFACE | 253

 MODEL INPUTS
The temperature model input is always available. 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
component (if any). For example, select Temperature (ht) to use the temperature
defined by the Heat Transfer in Fluids interface with the ht name.

CONVECTION
This section is available when the Convection check box is selected.

The velocity field for the convection of the solvent, which is used in the convective
term, needs to be specified as feature input. Select the source of the Velocity field u:

• Select User defined to enter values or expressions for the velocity components. This
input is always available.
• Select a velocity field defined by a Fluid Flow interface present in the model (if any).
For example, select Velocity field (spf) to use the velocity field defined by the Fluid
Properties node fp1 in a Single-Phase Flow, Laminar Flow interface with spf as the
Name.

DIFFUSION
Select a Material from the list (when applicable and available). The default is None.

Specify the Diffusion coefficient Di for each species. This can be a scalar value for
isotropic diffusion or a tensor describing anisotropic diffusion. Enter the values in the
field (one for each species).

MIGRATION IN ELECTRIC FIELD

Specify the Mobility and the Charge number of the ionic species. These properties affect
the migration of ionic species. 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 mobility, select User defined for the mobility um,i and enter one
value for each species.

Enter the Charge number zi (dimensionless, but requires a plus or minus sign) for each
species.

254 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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

Electric Insulation
The Electric Insulation node is the default boundary condition for the electric field. It
provides a boundary condition for the electric field that means that the boundary is
electrically insulated; that is, there is no current flowing across the boundary:

–n ⋅ i = 0 (3-108)

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

–n ⋅ Ji = 0

Initial Values
The Initial Values node adds initial values for the concentrations ci and the electric
potential V that can serve as an initial condition for a transient simulation or as an initial
guess for a nonlinear solver. Add more Initial Values nodes from the Physics toolbar.

INITIAL VALUES
Enter values or expressions for the initial value of the Concentration ci (SI unit: mol/
m3) (except the one that a mass constraint determines) and for the Electric potential V
(SI unit: V). The default concentration values are 0 mol/m3 and the default electric
potential is 0 V.

Reactions
In order to account for consumption or production of species, the Reactions node adds
rate expressions Ri, which appear on the right-hand side of the species transport
equations.

THE NERNST-PLANCK EQUATIONS INTERFACE | 255

 REACTIONS
Add a rate expression Ri (SI unit: mol/(m3·s)) for each of the species solved for. Enter
a value or expression in the field of the corresponding species.

Concentration
The Concentration node adds a boundary condition for the species concentrations: for
example the following condition specifies the concentration of species, ci:

c i = c i, 0

Set the concentration of all species except the one computed from the
electroneutrality condition, which ensures that the net charge is zero. See
Species.

CONCENTRATION
Specify the concentration ci (SI unit: mol/m3) for each species individually. Select the
check box for the species to specify the concentration, 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 that species’ mass fraction.

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

Flux
The Flux node can be used to specify the species flux across a boundary. The species
flux, for example at the surface of a electrode, is defined as:

– n ⋅ J i = J 0, i

where n denotes the normal unit vector to the boundary. The flux J0,i can be any
function of concentration and electric potential (and indeed temperature if heat
transfer is included in the model), often provided by a kinetic expression. In
electrochemistry, this function usually depends on concentration and exponentially on
the electric potential through either the Tafel equation or the Butler-Volmer
equation.

256 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

INWARD FLUX
Specify the inward species flux for each species individually. Select the check box for
the species to prescribe a flux and enter a value or expression for the Inward flux J0,i
(SI unit: mol/(m3·s)). To use another boundary condition for a specific species, click
to clear the check box for that species’ flux. Use a positive value for an inward flux.

Symmetry
The Symmetry node can be used to represents a boundaries where the concentration is
symmetric; that is, there is no species flux in the normal direction across the boundary:

–n ⋅ Ji = 0

This boundary condition is identical to that of the No Flux condition.

Inflow
The Inflow node adds a boundary condition for an inflow boundary, where the
concentration for all species is specified in the manner of c i = c i, 0 .

This condition is identical to the Concentration node, but is applied to all

species and cannot be applied to individual species.

CONCENTRATION
Specify the concentration ci (SI unit: mol/m3) of each species individually by entering
a value or expression in the corresponding field.

BOUNDARY CONDITION TYPE

The Concentration constraint is selected by default. This setting constrains the
concentration values on the boundary by the use of point-wise constraints. Flux
(Danckwerts) can be advantageous when high reaction rates are anticipated in the
vicinity to the inlet. This uses a flux boundary condition based on the velocity across
the boundary and the concentration values.

Danckwerts Inflow Boundary Condition

THE NERNST-PLANCK EQUATIONS INTERFACE | 257

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

Outflow
The Outflow condition assumes that convection and migration is the dominating
transport mechanism across the outflow boundary, and therefore that diffusive
transport can be ignored, that is:

n ⋅ ( – D ∇c ) = 0

Flux Discontinuity
The Flux Discontinuity node represents a discontinuity in the species flux across an
interior boundary:

– n ⋅ ( N u – N d ) = N 0, i N = ( ci u + Ji )

where the value of N0,i specifies the size of the flux jump, evaluated from the up to the
down side of the boundary. This boundary condition is only available on interior
boundaries.

FLUX DISCONTINUITY
Specify the jump in species flux, using a positive value for increasing flux when going
from the down to the up side of the boundary. The normal direction (nx,ny,nz)
((nr,nz) in axisymmetric models) points in the direction from the downside toward
the upside of an internal boundary and can be plotted for visualization.

Select the check boxes for the species to specify a Flux discontinuity N0 (SI unit: mol/
(m2·s)) and enter a value or expression for the mass flux jump in the corresponding
field. To use another boundary condition for a specific species, click to clear the check
box for that species’ flux discontinuity.

Current Density
The Current Density node provides a boundary condition for the electric field which
makes it possible to set the total current density at a boundary. The condition is
defined as:

–n ⋅ i = i0 (3-109)

258 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

where n denotes the normal vector to the boundary and i0 is the inward current
density.

It is common to combine this boundary condition with concentration

conditions for the species. Such a combination is useful in cases where the
flow in an electrochemical cell is vigorous and in cases where the whole
cell is not treated in a model, most often when the opposite electrode is a
far away. Half-cell investigations are very applicable for this type of
condition.

INWARD CURRENT DENSITY

Specify the current density i0 (SI unit: A/m2). Use a positive value for an inward
current flow.

Current Discontinuity
The Current Discontinuity node represents a discontinuity in the current density across
an internal boundary:

–n ⋅ ( iu – id ) = i0 i = F  zi ( – Di ∇ci – zi um, i Fci ∇V )

k=1

where the value of i0 specifies the size of the current density jump evaluated from the
up to the down side of the boundary. This boundary condition is only available on
interior boundaries.

CURRENT DISCONTINUITY
2
Specify i0 (SI unit: A/m ), the jump in current density, using a positive value for
increasing current density when going from the up to the down side of the boundary.
The normal direction (nx,ny,nz) ((nr,nz) in axisymmetric models) points in the
direction from the downside toward the upside of an interior boundary and can be
plotted for visualization.

Open Boundary
Use the Open Boundary node to set up mass transport across boundaries where both
convective inflow and outflow can occur. Specify an exterior species concentration on

THE NERNST-PLANCK EQUATIONS INTERFACE | 259

 parts of the boundary where fluid flows into the domain. A condition equivalent to the
Outflow node applies to 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 provided as a Model Input to the
Nernst-Planck Equations interface.

The potential is assumed to be constant in the normal direction across the

boundary.

EXTERIOR CONCENTRATION
Enter a value or expression for the exterior concentration c0,c2 (SI unit: mol/m3).

Reference for the Nernst Planck Equations Interface

1. R. Codina, “A Discontinuity-capturing Crosswind-dissipation Stabilization for the
Finite Element Solution of the Convection-diffusion Equation”, Computer Methods
in Applied Mechanics and Engineering, vol. 110, pp. 325–342, 1993.

260 | CHAPTER 3: 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 ( )

(with Migration enabled), which solves for the Nernst-Planck equations without
charge neutrality, and The Electrostatics Interface( ), that solves for the Poisson’s
equation.

A ( ) multiphysics node is also added. This node computes the local space charge,
based on the local concentrations and species charges in the Transport of Diluted
Species interface, and adds it to Poisson’s Equation in the Electrostatics interface.

Finally, a ( ) multiphysics node is added that applies the potential dependent

variable in the Electrostatics interface into the migration term of the Transport of
Diluted Species interface.

• The Multiphysics Branch in the COMSOL Multiphysics

Reference Manual.
• The Transport of Diluted Species Interface.
• The Electrostatics Interface

Diffuse Double Layer: Application Library path

Chemical_Reaction_Engineering_Module/Electrokinetic_Effects/
diffuse_double_layer

THE NERNST-PLANCK-POISSON EQUATIONS INTERFACE | 261

 The Electrophoretic Transport
Interface
The Electrophoretic Transport (el) interface ( ), found under the Chemical Species
Transport branch ( ), is used to solve for the electrophoretic transport of an
arbitrarily number of species in water-based system, subject to potential gradients. The
species transported can be any combination of weak and strong acids and bases,
ampholytes and uncharged species. The transport of masses and charge is based on the
Nernst-Planck equations for molecular transport, in combination with
electroneutrality, dissociation equilibria for weak acids, bases and ampholytes as well as
the water auto-ionization reaction.

The physics interface can simulate most forms of electrophoresis modes, such as zone
electrophoresis, isothachophoresis, isoelectric focusing and moving boundary
electrophoresis.

Gel electrophoresis can be simulated by the inclusion of immobile charged species.

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

The dependent variables are the electrolyte potential, and the molar concentrations of
the included species, added individual by each species node in the model tree.

Zone Electrophoresis: Application Library path

Chemical_Reaction_Engineering_Module/Electrokinetic_Effects/
zone_electrophoresis

SETTINGS
The Label is the default physics interface name.

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

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

262 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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

OUT-OF-PLANE THICKNESS

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

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

CROSS SECTIONAL AREA

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

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

• By default, the Convection check box is selected. Clear the check box to disable
convective transport.
• The Mass transfer in porous media check box activates functionality specific to species
transport in porous media. When selected, the Porous Matrix Properties node can
be added to a domain to specify the electrolyte volume fraction and tortuosity, and
the Effective Transport Parameter Correction sections are enabled in the species
nodes.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 263

 CONSISTENT STABILIZATION
To display this sections, click the Show button ( ) and select Stabilization.

• When the Crosswind diffusion check box is selected, a weak term that reduces
spurious oscillations is added to the transport equation. The resulting equation
system is always nonlinear.
• For both Streamline diffusion and Crosswind diffusion, select an Equation residual.
Approximate residual is the default and means that derivatives of the diffusivity are
neglected. This setting is usually accurate enough and is computationally faster. If
required, select Full residual instead.

INCONSISTENT STABILIZATION
To display this section, click the Show button ( ) and select Stabilization. By default,
the Isotropic diffusion check box is not selected, because this type of stabilization adds
artificial diffusion and affects the accuracy of the original problem. However, this
option can be used to get a good initial guess for under-resolved problems.

ADVANCED SETTINGS
To display this section, click the Show button ( ) and select Advanced Physics Options.
Normally these settings do not need to be changed. Select a Convective term —
Nonconservative form (the default) or Conservative form. The conservative formulation
should be used for compressible flow.

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

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.

264 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

The flux variables affected in the interface are:

• <name>.nIl, where <name> is the name of the interface (default is el), set on the
interface top node. This is the normal electrolyte current density.
• <name>.ntflux_<species_name> is the Species name (see Common Settings for
the Species nodes in the Electrophoretic Transport Interface below). This is the
normal total flux for each species.

Also the Apply smoothing to boundary fluxes check box is available if the previous check
box is checked. The smoothing can provide a more well-behaved flux value close to
singularities.

For details about the boundary fluxes settings, see Computing Accurate Fluxes in the
COMSOL Multiphysics Reference Manual.

Regarding the Value type when using splitting of complex variables, see Splitting
Complex-Valued Variables in the COMSOL Multiphysics Reference Manual.

DEPENDENT VARIABLES
The dependent variable name for the electrolyte potential variable is phil by default.

The name of the concentration dependent variables are named as el.xxx, where the el is
the name of the interface as set above, and the xxx string is controlled by the Species
name setting on the individual species nodes.

FURTHER READING

• Theory for the Electrophoretic Transport Interface

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

THE ELECTROPHORETIC TRANSPORT INTERFACE | 265

 Common Settings for the Species nodes in the Electrophoretic Transport
Interface
The interface features the following species nodes, applicable on the domain level:

• Ampholyte
• Fully Dissociated Species
• Uncharged Species
• Weak Acid
• Weak Base
Each species node add a dependent variable for the concentration. The initial and
boundary condition, as well as adding additional source reaction terms, for each
species concentration is controlled by adding subnodes to the species nodes:

• Concentration
• Flux
• Inflow
• Initial Concentration
• No Flux
• Outflow
• Species Source

The Ampholyte, Weak Acid and Weak Base are dissociation species and may define an
arbitrary number of dissociation steps. Each dissociation step is defined by it’s pKa (the
acid equilibrium constant) parameter. For the weak bases the pKa refers to the acid
constant of the conjugate acid. Each dissociation step adds one additional subspecies
concentration variable so that the concentration dependent variable represents the sum
of all subspecies, and initial and boundary conditions are defined with respect to this
total concentration.

All species node have a setting for the Species name, which needs to be unique. The
species name is used for naming of all related variables of the species. For species nodes
not defining any subspecies, the concentration variables are named as
<name>.c_<species_name> where <name> is the name of the interface (default is el),
set on the interface top node, and <species_name> is the Species name. For
dissociation species nodes defining multiple subspecies, the concentration nodes are
named as <name>.c<X>_<species_name> where <X> is the integer from 1 up to the

266 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

total number of subspecies. Note that the Solvent node automatically defines the
concentration variables for protons (<name>.cH) and hydroxide ions (<name>.cOH).

All species except the Uncharged Species carry charge and contribute to the total
electrolyte current which is used in the equation for solving the electrolyte potential.

The Immobile Species check box can be used to lock the concentration of a species, to,
for instance, define the immobile charges in a ion-selective membrane or a gel. When
the check box is enabled the concentration of the species is not added as a dependent
variable to the model; instead the concentration will be set to the value provided in the
Concentration field. The contribution to the electrolyte current for immobile species is
zero.

Diffusion and Migration Settings

All species, except when the Immobile Species check box has been enabled, may be
transported by diffusion, and charged species are also transported by migration in the
electric field.

For dissociation species you may choose to set the transport parameters to be the Same
for all species appearing in the different dissociation steps, or you may use Individual
settings for each subspecies.

Typically the mobilities and diffusivities for small species are related by the
Nernst-Einstein relation, and when this relation is enabled you can choose whether to
specify either the Diffusivity (SI unit: m2/s) or the Mobility (SI-unit: s·mol/kg). The
Debye-Hückel-Henry relation is commonly used for larger molecules, such as proteins.

Note: There are other definitions of the migration transport equations in literature
which use mobilities expressed in m2/(V·s), whereas COMSOL Multiphysics uses
s·mol/kg. To convert mobilities expressed in m2/(V·s) to the corresponding values in
s·mol/kg, you typically divide by the Faraday constant, F_const (96485 C/mol).

EFFECTIVE TRANSPORT PARAMETER CORRECTION

If Mass transfer in porous media is enabled on the interface top node, you may use the
settings of this section in the species nodes to account for the changed mass transport
in a porous domain due to the lowered porosity and the increased tortuosity.

The default correction model is Bruggeman, which multiplies the diffusivity and
mobility values by the porosity to the power of 1.5. The porosity of a domain is set by
the Porous Matrix Properties node.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 267

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

The Debye-Hückel-Henry relation makes use of the ionic strength for calculating the
species mobility from the diffusivity. All charged species contribute to the ionic
strength, either assuming the species contributing to an Ideal solution or by using the
Lindestrøm-Lang assumption. The latter is usually used for macromolecules.

Domain, Boundary, and Pair Nodes for the Electrophoretic Transport

Interface
The interface has the following domain, boundary, and pair nodes, listed in
alphabetical order, available from the Physics ribbon toolbar (Windows users), Physics
context menu (Mac or Linux users), or by right-clicking to access the context menu
(all users).

To add a node, go to the Physics toolbar, no matter what operating system

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

• Ampholyte • No Flux
• Concentration • Outflow
• Current • Porous Matrix Properties
• Current Density • Potential
• Current Source • Protein
• Flux • Species Source
• Fully Dissociated Species • Solvent
• Inflow • Uncharged Species
• Initial Concentration • Weak Acid
• Initial Potential • Weak Base
• Insulation

268 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

 For axisymmetric components, COMSOL Multiphysics takes the axial
symmetry boundaries (at r = 0) into account and automatically adds an
Axial Symmetry node that is valid on boundaries representing the
symmetry axis.

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

Solvent
The settings of this node are used to define the properties of the aqueous solvent.

If Convection is enabled on the interface top node, you can specify the Velocity field
(m/s) as user defined input using analytical expressions or the velocity field variables
solved for by a separate physics interface.

The Solvent node automatically defines the concentration variables and for protons
(<name>.cH) and hydroxide ions (<name>.cOH), and the corresponding flux
expressions. See Diffusion and Migration Settings for how to set up the transport
parameters for the proton and hydroxide ions.

In the Solvent Properties section you can modify the Dynamic viscosity (Pa·s) and
Relative permittivity (unitless) values. The Built in and default values are applicable to
water. These parameters are used when calculating mobilities according to the
Debye-Hückel-Henry relation in the species nodes.

In the Water Self-Ionization section you can change the default Built in expression for
the Water self-ionization constant, pKw (unitless), to any user defined expression.

Porous Matrix Properties

Use this node, available if Mass transfer in porous media has been enabled on the
interface top-node, to define the Porosity (electrolyte volume fraction) and Tortuosity
of a domain.

The porosity should be a number between 0 and 1.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 269

 Fully Dissociated Species
Use this node to define a fully dissociated charged species, such as strong bases and
acids.

The Charge number, Z0 (unitless), defines the species charge.

See also Common Settings for the Species nodes in the Electrophoretic Transport
Interface and Diffusion and Migration Settings.

Uncharged Species
Use this node to define a species that does not carry any charge, nor is impacted by the
electric field.

See also Common Settings for the Species nodes in the Electrophoretic Transport
Interface and Diffusion and Migration Settings.

Weak Acid
The Weak acid node supports multiple dissociation steps, where the acid of the first
dissociation step is uncharged.

The species may be either Monoprotic, subject to one dissociation step only, or
Polyprotic. For the latter case any Number of dissociation steps larger than one may be
used.

See also Common Settings for the Species nodes in the Electrophoretic Transport
Interface and Diffusion and Migration Settings.

Weak Base
The Weak base node supports multiple dissociation steps, where the base of the last
dissociation step is uncharged.

The species may be either Monoprotic, subject to one dissociation step only, or
Polyprotic. For the latter case any Number of dissociation steps larger than one may be
used.

Note that the pKa refers to the acid constant of the conjugate acid of the weak base.

See also Common Settings for the Species nodes in the Electrophoretic Transport
Interface and Diffusion and Migration Settings.

270 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

Ampholyte
Use the Ampholyte node generically to define any species where the average charge
depends on the pH of the solution. The Dissociation model may be based either on a
set of Equilibrium constants or an Average charge.

When using the Equilibrium constants the Base charge in last dissociation step, Z0
(unitless), needs to be set.

The Average charge, Z (unitless) parameter is typically a function of pH and may be

added as an analytical function or an interpolation polynomial under Definitions. The
average squared charge, used in the electrolyte potential equation, is calculated
automatically based on Z .

See also Common Settings for the Species nodes in the Electrophoretic Transport
Interface and Diffusion and Migration Settings.

Protein
Use the Protein node to define macromolecules. The features of the Protein node are
similar to the Ampholyte node, but with the default settings applicable for larger
molecules.

See also Common Settings for the Species nodes in the Electrophoretic Transport
Interface and Diffusion and Migration Settings.

Current Source
To make this node available, click the Show button ( ) and select Advanced Physics
Options.

Use this node to add a current source in a domain. A current source may appear in a
domain in homogenized porous electrode modeling, but should normally not be used.

Initial Potential
Use this node to specify the Initial Value of the electrolyte potential for the solver.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 271

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

This node is typically used to model electrode surfaces or boundaries facing an

electrolyte reservoir (containing an electrode).

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

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

This node is typically used to model electrode surfaces where the electrode kinetics
depends on the electrolyte potential.

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

Insulation
The Insulation boundary condition describes the walls of a cell or the boundaries of the
cell that do not face an electrode (or a reservoir containing an electrode). The
boundary condition imposes the following equation:

il ⋅ n = 0

Potential
Add the Potential node on a boundary to set a fixed potential. This node is typically
used to model electrode surfaces or boundaries facing an electrolyte reservoir.

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

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

272 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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

This node may be added as a subnode to any species node. See also Common Settings
for the Species nodes in the Electrophoretic Transport Interface.

In order to account for consumption or production of species, for example in porous

electrodes or as a result of reversible reactions, the Species Source node adds source
terms expressions S (SI unit: mol/(m3·s) to the right-hand side of the transport
equation of the parent species.

Initial Concentration
This node may be added as a subnode to any species node. See also Common Settings
for the Species nodes in the Electrophoretic Transport Interface.

This node specifies the initial value for the Concentration, c (mol/m3), of the parent
species. This value serve as the initial condition for a transient simulation. The value
also serves as a start guess for stationary problems.

You can use spatially dependent functions (such as smoothed step functions) available
under Definitions when defining the Concentration expression to specify different
concentrations in different parts of the geometry. You can also use additional Initial
Values node and modify the Selection to set different values for different domains.

Concentration
This node may be added as a subnode to any species node. See also Common Settings
for the Species nodes in the Electrophoretic Transport Interface

This condition node adds a boundary condition for the parent species concentration.
Use the node to, for instance, specify the inlet concentration at the boundary facing a
electrolyte reservoir.

No Flux
This node may be added as a subnode to any species node. See also Common Settings
for the Species nodes in the Electrophoretic Transport Interface.

THE ELECTROPHORETIC TRANSPORT INTERFACE | 273

 This node is the default boundary condition on exterior boundaries. It represents
boundaries where no mass flows in or out of the boundaries. Hence, the total flux is
zero.

Flux
This node may be added as a subnode to any species node. See also Common Settings
for the Species nodes in the Electrophoretic Transport Interface.

This node can be used to specify the species inward flux across a boundary. The flux
can represent a flux from or into a much larger surrounding environment, a phase
change, or a flux due to chemical reactions.

INWARD FLUX
Enter a value or expression for the species mass flux J0. Use a minus sign when
specifying a flux directed out of the system.

External convection
Set Flux type to External convection to prescribe a flux to or from an exterior domain
(not modeled) assumed to include convection. The exterior can for example include a
forced convection to control the temperature or to increase the mass transport. In this
case the prescribed mass flux corresponds to

J0 = kc ( cb – c )

where kc is a mass transfer coefficient and cb is the bulk concentration, the typical
concentration far into the surrounding exterior domain.

Inflow
This node is available when you select the Convection check box on the physics interface
Settings window.

Use this node to specify the species concentrations at an inlet boundary.

BOUNDARY CONDITION TYPE

The option Concentration constraint constrains the concentration values on the
boundary by the use of pointwise constraints. When using this option the boundary
condition is identical to the Concentration node.

The other option, Flux (Danckwerts) can be more stable and fast to solve when high
reaction rates are anticipated in the vicinity of the inlet. Oscillations on the solutions

274 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

can also be avoided in such cases. The latter condition uses a flux boundary condition
based on the velocity across the boundary and the concentration values.

Outflow
Set this condition at outlets where species are transported out of the model domain by
migration or fluid motion. It is assumed that migration and convection is the
dominating transport mechanism across outflow boundaries, and therefore that
diffusive transport can be ignored, that is:

n ⋅ ( – D ∇c ) = 0

THE ELECTROPHORETIC TRANSPORT INTERFACE | 275

 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.

276 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

Enter the Number of bulk species. Use the Add bulk concentration ( ) and Remove bulk
concentration ( ) buttons as needed. The same number of Bulk concentrations cb,
cb2, cb3, … are then listed in the table.

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

For more information about these settings, see the Discretization section under The
Transport of Diluted Species Interface.

CONSISTENT AND INCONSISTENT STABILIZATION

To display these sections, click the Show button ( ) and select Stabilization.

By default the Compensate for boundary stretching check box is selected for the Surface
Properties node. This section is then used to stabilize the tangential mesh velocity
term.

When the Compensate for boundary stretching check box is cleared (not selected), and
for fixed geometries or moving geometries, the stabilization has no effect.

See Surface Reaction Equations on Deforming Geometries for more information.

• Boundary, Edge, Point, and Pair Nodes for the Surface Reactions
Interface
• Theory for the Surface Reactions Interface

Protein Adsorption: Application Library path

Chemical_Reaction_Engineering_Module/Mixing_and_Separation/
protein_adsorption

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 | 277

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

Surface Properties
Use the Surface Properties node to define the density of sites, the site occupancy
number, and the surface diffusion.

SPECIES CONSERVATION ON DEFORMING GEOMETRY

The Compensate for boundary stretching check box is selected by default. Click to clear
the check box if required.

SITES
Enter a value or expression for the Density of sites Γs (SI unit: mol/m2). The default
is 2 x 10-5 mol/m2.

Enter a Site occupancy number σi (dimensionless), indicating how many surface sites a
surface species block upon adsorption.

This section is only present if the number of surface species is 1 or higher.

278 | CHAPTER 3: 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 Anisotropic
depending on the characteristics of the surface, and then enter values or expressions in
the field or matrix.

This section is only present if the number of surface species is 1 or higher.

BULK SPECIES
For each bulk species enter the Molar mass Mi (SI unit: kg/mol) and the Density ρi
(SI unit: kg/m3). The default molar mass is 0.144 kg/mol and the default density is
5320 kg/m3).

This section is only present if the number of bulk species is 1 or higher.

Surface Reaction Equations on Deforming Geometries

Initial Values
The Initial Values node allows the initial value or guess for the surface and bulk
concentrations.

INITIAL VALUES
Based on the number of surface species and number of bulk species entered for the
physics interface under Dependent Variables section, enter values for the same number
of Surface concentration cs, cs2, cs3,... (SI unit: mol/m2) and Bulk concentration cb,
cb2, cb3,... (SI unit: mol/m2) in each field.

Reactions
The Reactions node adds rate expression terms to the species transport equations in
order to account for consumption or production of species due to reactions.

REACTION RATE FOR SURFACE SPECIES

Add a reaction rate expression, Rs,cs1,cs2...(SI unit: mol/(m2·s)), for each surface
species taking part in a surface reaction.

THE SURFACE REACTIONS INTERFACE | 279

 This section is only present if the number of surface species is 1 or higher.

REACTION RATE FOR BULK SPECIES

Add a reaction rate expression, Rb,cb1,cb2...(SI unit: mol/(m2·s)), for each bulk species
taking part in a surface reaction.

This section is only present if the number of bulk species is 1 or higher.

Surface Concentration
Use the Surface Concentration node to set the surface concentrations for one or more
species on an edge (3D components) or a point (2D and 2D axisymmetric
components).

SURFACE CONCENTRATION
Select each species check box as needed and enter a value or expression for each species
concentration, cs,0,cs1,cs2... (SI unit: mol/(m2·s)).

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

280 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

The Reacting Flow Multiphysics
Interface
Reacting Flow is a predefined multiphysics interface, available in the Chemical
Reaction Engineering Module, that couples fluid flow with mass transport and
reactions.

Selecting Laminar Flow under the Chemical Species Transport>Reacting Flow branch of
the Model Wizard or Add Physics windows, a Laminar Flow interface and a Transport of
Concentrated Species interface are added to the Model Builder.

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 easy set up of models.

In this section:

• The Reacting Laminar Flow Interface

• The Reacting Flow Coupling Feature
• Physics Interface Features

The Reacting Laminar Flow Interface

The Reacting Laminar Flow multiphysics interface is used to simulate laminar flow
coupled to species transport in a gas or liquid.

It combines the Laminar Flow, and Transport of Concentrated Species interfaces. The
Reacting Flow multiphysics coupling, which is added automatically, couples fluid flow
and mass transport. The fluid flow can either be free flow or flow in a porous medium.
The species transport supports both a mixture, where the concentrations are of
comparable order of magnitude, and low-concentration solutes in a solvent.

The interface can be used for stationary and time-dependent analysis in 2D, 2D axial
symmetry, and 3D.

On the constituent physics interfaces:

The equations solved by the Laminar Flow interface are the Navier-Stokes equations for
conservation of momentum and the continuity equation for conservation of mass. A
Fluid Properties feature is active by default on the entire interface selection. A Fluid and

THE REACTING FLOW MULTIPHYSICS INTERFACE | 281

 Matrix Properties feature can be added in order to model flow in porous media by
solving the Brinkman equations.

The Transport of Concentrated Species interface solves for an arbitrary number of mass
fractions. The species equations include transport by convection, diffusion and,
optionally, migration in an electric field.

The Reacting Laminar Flow interface triggers pseudo time stepping for the
flow equations when Use pseudo time stepping for stationary equation form
in the Fluid Flow interface is set to Automatic from physics.

The Reacting Flow Coupling Feature

Use the Reacting Flow ( ) multiphysics coupling to simulate mass transport and
reactions in a gas or liquid mixture where the fluid flow can be dependent on the
mixture composition.

DOMAIN LEVEL SYNCHRONIZATION

The Reacting Flow coupling synchronizes the features from a Single-Phase Flow, or
Brinkman Equations, interface and a Transport of Concentrated Species interface.
When added, the density in the Single-Phase Flow interface is automatically
synchronized to the one defined by the Transport of Concentrated Species interface.
Conversely, the velocity field used by the latter interface is synchronized to the one
computed in the former interface.

THE STEFAN VELOCITY

The Reacting Flow coupling feature automatically couples mass transfer on boundaries
and applies a corresponding velocity contribution for the flow. Prescribing a net mass
boundary flux in the Transport of Concentrated Species interface, either using a Flux or
Mass Fraction feature, the Reacting Flow feature computes The Stefan Velocity and
applies this in Wall features using the same selection.

MASS TRANSFER TO OTHER PHASES IN POROUS MEDIA

When coupled to the Brinkman Equations interface, the Reacting Flow node
automatically computes the net mass source or sink in a Reactions (when Mass transfer
to other phases is enabled) node in the Transport of Concentrated Species interface and
adds the corresponding source/sink to the momentum equations of the Fluid and
Matrix Properties domains.

282 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

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 rf1.

DOMAIN SELECTION
The Reacting Flow coupling is automatically defined on the intersection of the
selections for the coupled interfaces.

The Selection list displays the domains where the coupling feature is active.

COUPLED INTERFACES
This section defines the physics involved in the multiphysics coupling. The Fluid flow
and Species transport lists include all applicable physics interfaces.

The default values depend on how this coupling node is created.

• If it is added from the Physics ribbon (Windows users), Physics contextual toolbar
(Mac and Linux users), or context menu (all users), then the first physics interface
of each type in the component is selected as the default.
• If it is added automatically when a multiphysics interface is chosen in the Model
Wizard or Add Physics window, then the two participating physics interfaces are
selected.

You can also select None from either list to uncouple the node from a physics interface.
If the physics interface is removed from the Model Builder, for example Laminar Flow is
deleted, then the Species transport list defaults to None as there is nothing to couple to.

Click the Go to Source buttons ( ) to move to the main physics interface node for
the selected physics interface.

Click the Show or Hide Physics Properties Settings button ( ) to toggle the display of
physics properties settings affecting the coupling feature. When a turbulence model is
used, turbulent mass transfer is automatically accounted for (see the settings in the
Turbulence section below). Using Reacting Flow, the mass transfer treatment at walls
follows that applied for the fluid flow. Therefore the Wall treatment setting is also
displayed when using a turbulence model. For more information on turbulent mass

THE REACTING FLOW MULTIPHYSICS INTERFACE | 283

 transfer at walls, see the section Mass Transport Wall Functions in the CFD Module
User’s Guide.

If a physics interface is deleted and then added to the model again, then
in order to reestablish the coupling, you need to choose the physics
interface again from the Fluid flow or Species transport lists. This is
applicable to all multiphysics coupling nodes that would normally default
to the once present interface. See Multiphysics Modeling Approaches in
the COMSOL Multiphysics Reference Manual.

TURBULENCE
When the fluid flow interface uses a turbulence model, select an option from the Mass
transport turbulence model list — Kays-Crawford, High Schmidt Number, or User-defined
turbulent Schmidt number.

For User-defined turbulent Schmidt number, enter a Turbulent Schmidt number ScT
(dimensionless).

The turbulent mass transfer added to the mass fraction equations is defined as

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.

Note, since the Reacting Flow coupling feature adds the turbulent mass transport, it
should not be combined with a Turbulent Mixing feature (subfeature to Transport
Properties in the Transport of Concentrated Species interface).

Physics Interface Features

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

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

operating system you are using.

284 | CHAPTER 3: 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 MULTIPHYSICS INTERFACE | 285

 The Reacting Flow in Porous Media
Multiphysics Interface
The Chemical Reaction Engineering 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 set up of models.

In this section:

• The Reacting Flow in Porous Media, Transport of Diluted Species Interface

• The Reacting Flow in Porous Media, Transport of Concentrated Species Interface
• The Reacting Flow, Diluted Species Coupling Feature
• The Reacting Flow Coupling Feature
• Physics Interface Features

The Reacting Flow in Porous Media, Transport of Diluted Species

Interface
The Reacting Flow in Porous Media, Transport of Diluted Species interface ( ) is used
to study the flow and chemical composition of a gas or liquid moving through the
interstices of a porous medium.

It combines the Brinkman Equations, and Transport of Diluted Species in Porous Media
interfaces. The Reacting Flow, Diluted Species multiphysics coupling feature, which is
added automatically, couples the fluid flow and mass transport.

The interface can be used for stationary and time-dependent analysis in 2D, 2Daxi and
3D.

286 | CHAPTER 3: 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 Fluid and Matrix
Properties feature is active by default on the entire interface selection.

The Transport of Diluted Species in Porous Media interface computes the species
concentration in free and porous media, assuming that the species are of solutes,
dissolved in a solvent of significantly higher concentration. The species equations
include transport by convection, diffusion and, optionally, migration in an electric
field.

The Reacting Flow in Porous Media, Transport of Concentrated

Species Interface
The Reacting Flow in Porous Media, Transport of Concentrated Species interface ( ) is
used to study the flow and chemical composition of a gas or liquid moving through
the interstices of a porous medium. The fluid can consist of a mixture of species where
the individual concentrations are of comparable order of magnitude.

It combines the Brinkman Equations, and Transport of Concentrated Species interfaces.

The Reacting Flow multiphysics coupling feature, which is added automatically, couples
the fluid flow and mass transport.

The interface can be used for stationary and time-dependent analysis in 2D, 2Daxi and
3D.

On the constituent physics interfaces:

The Brinkman Equations interface computes the fluid velocity and pressure fields of
single-phase flow in porous media in the laminar flow regime. A Fluid and Matrix
Properties feature is active by default on the entire interface selection.

The Transport of Concentrated Species interface solves for an arbitrary number of mass
fractions in free and porous media. In the current multiphysics interface a Porous Media
Transport Properties feature is active by default on the entire interface selection.

The Reacting Flow, Diluted Species Coupling Feature

For the settings of this feature see The Reacting Flow, Diluted Species Coupling
Feature in the COMSOL Multiphysics Reference Manual.

THE REACTING FLOW IN POROUS MEDIA MULTIPHYSICS INTERFACE | 287

 The Reacting Flow Coupling Feature
For the settings of this feature see The Reacting Flow Coupling Feature.

Physics Interface Features

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

BRINKMAN EQUATIONS
The available physics features for The Brinkman Equations interface are listed in the
Domain, Boundary, Point, and Pair Nodes for the Brinkman Equations Interface
section in the CFD Module User’s Guide.

TRANSPORT OF DILUTED SPECIES

The available physics features for The Transport of Diluted Species interface are listed
in the 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.

288 | CHAPTER 3: CHEMICAL SPECIES TRANSPORT INTERFACES

 4

Fluid Flow Interfaces

The functionality for simulating fluid flow in free, porous media is found under
the Fluid Flow branch ( ) when adding a physics interface.

The documentation of the available interfaces and features can be found in CFD
Module User’s Guide in the chapters Single-Phase Flow Interfaces and Porous
Media and Subsurface Flow Interfaces.

289
 Modeling Fluid Flow
In this section:

• Available Physics Interfaces

• Coupling to Other Physics Interfaces

Available Physics Interfaces

This module primarily models the transport and conversion of mass in chemical
reactors and other reacting systems. Many of these applications include transport
through convection, and the module includes a number of physics interfaces for the
simulation of fluid flow, particularly within porous media. As with all other physical
descriptions simulated by COMSOL Multiphysics, any description of fluid flow can be
directly coupled to any other physical process. This is particularly relevant for systems
based on turbulent or multiphase flow, which are supported by the CFD Module. For
detailed descriptions of the fluid-flow interfaces listed below, see the CFD Module
User’s Guide.

The Fluid Flow branch ( ) has a number of subbranches to describe momentum

transport. The Laminar Flow Interface ( ), found under the Single-Phase Flow
branch ( ) when adding a physics interface, is used to model laminar flow described
by the Navier-Stokes equations. It is also possible to extend this physics interface to
study nonisothermal or non-Newtonian flow.

The Creeping Flow Interface ( ), also under the Single-Phase Flow branch ( ), is
used to model flow fluid flows at very low Reynolds numbers, also referred to as Stokes
flow. This typically occurs in fluid systems with high viscosity or small geometrical
length scales (for example in microfluidics and MEMS devices).

The rest of the available physics interfaces for fluid flow are found under the Porous
Media and Subsurface Flow branch ( ).

The Darcy’s Law Interface ( ) is used to model fluid movement through interstices
in a porous medium where a homogenization of the porous and fluid media into a
single medium is done. This physics interface combines the continuity equation and an
equation of state for the pore fluid (or gas), can be used to model low velocity flows,
for which the pressure gradient is the major driving force.

290 | CHAPTER 4: FLUID FLOW INTERFACES

Darcy’s law can be used in porous media where the fluid is mostly influenced by the
frictional resistance within the pores. When the size of the interstices are larger and the
fluid is influenced by itself, the kinetic potential from fluid velocity, pressure, and
gravity must be also be considered, and The Brinkman Equations Interface ( ) is the
appropriate physics interface to use.

The Brinkman equations extend Darcy’s law to describe the dissipation of the kinetic
energy by viscous shear, similar to the Navier-Stokes equation. Consequently, they are
well suited to transitions between slow flow in porous media, governed by Darcy’s law,
and fast flow in channels described by the Navier-Stokes equations. The equations and
boundary conditions that describe these types of phenomena are also found in The
Free and Porous Media Flow Interface ( ).

The next section briefly discusses coupling to other physics interfaces.

Coupling to Other Physics Interfaces

Often, you are simulating applications that couple fluid flow in free porous media to
another type of phenomenon described in another physics interface. This can include
chemical reactions and mass transport, as covered in the Chemical Species Transport
branch, or energy transport in porous media found in the Heat Transfer branch.

More advanced descriptions of fluid flow, such as turbulent and multiphase flow, can
be found in the CFD Module. More extensive descriptions of heat transfer, such as that
in turbulent flow or systems including radiation, can be found in the Heat Transfer
Module. Furthermore, some applications that involve electrochemical reactions and
porous electrodes, particularly in electrochemical power source applications, are better
handled by the Batteries & Fuel Cells Module.

MODELING FLUID FLOW | 291

292 | CHAPTER 4: FLUID FLOW INTERFACES
 5

Heat Transfer Interfaces

The functionality for simulating heat transfer in free and porous media is found
under the Heat Transfer branch ( ) when adding a physics interface.

The documentation of all features in the Heat Transfer in Porous Media interface
can be found in the Heat Transfer Module User’s Guide, in the chapter Heat
Transfer Interfaces.

293
 Modeling Heat Transfer
Available Physics Interfaces
Heat transfer is an important part of chemical reaction engineering. Most chemical
reactions either require or produce heat, which in turn affects both the reactions
themselves and other physical processes connected to the system.

The heat transfer branch includes a number of physics interfaces for the simulation of
heat transfer, particularly in porous media. 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 important for systems based
on chemical reactions and mass transfer, along with fluid flow.

You can manipulate these physics interfaces with respect to including source and sink
terms or, in other words, account for exothermic or endothermic chemical reactions.

If you also have the Heat Transfer Module there are additional Heat
Transfer interface features, such as radiation, available.

Coupling Heat Transfer with Other Physics Interfaces

The Reaction Engineering Interface includes support for setting up and simulating
chemical reactions, including reaction kinetics through the temperature-dependent
Arrhenius expression and mass action law. This physics interface also has support for
including and calculating thermodynamic data as temperature-dependent expressions.
The Reaction Engineering interface can generate a space-dependent model using any
heat transfer interface to benefit from the bidirectional dependence between heat
transfer and chemical reactions.

More advanced descriptions of fluid flow, such as turbulent and multiphase flow,
require the CFD Module. In addition, the Heat Transfer Module also includes more
detailed descriptions and tools for simulating energy transport, such as radiation.

294 | CHAPTER 5: HEAT TRANSFER INTERFACES

 6

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

295
 Using Thermodynamic Properties
In this section:

• Workflow for Thermodynamics Property Calculations

• Thermodynamics
• Thermodynamic System
• External Thermodynamic Packages
• External Thermodynamic System
• Exporting and Importing Thermodynamic Systems
• Species Property
• Mixture Property
• Equilibrium Calculation
• Evaluating a Property Function in a Physics Interface
• 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 in the Chemical Reaction Engineering
Module makes it possible to calculate physical properties such as heat capacity, thermal
conductivity, density, diffusivity, and equilibrium compositions of two phases at
equilibrium. These 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 in Chemical Reaction Engineering Module

involves the following main steps:

296 | CHAPTER 6: THERMODYNAMICS

1 Add a Thermodynamics node and configure a thermodynamic system to add
properties for a selected set of chemical compounds, called chemical species in this
manual. Two types of thermodynamic systems can be created:
- 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 how to enable the use of external
packages see the Installing External Thermodynamic Packages–An Example.

2 If you use the Reaction Engineering interface or the Chemistry interface, link
chemical species in these interfaces with the chemical species in the thermodynamic
system. The required property parameters and functions are automatically added
and visualized as nodes under the corresponding Thermodynamic System node.
3 As an alternative to step 2 above, you can also set up functions or constants manually
for a thermodynamic system. You can, for example, create a function for the density
of a fluid for use in a fluid flow interface without having to use the Chemical
Reaction Engineering or the Chemistry interfaces. You can also define mixture
functions that depend on the composition of a mixture, for example for density,
enthalpy, or heat capacity.
4 Both alternatives in steps 3 and 4 above allow you to use the functions defined by a
thermodynamic system in any physics interface in COMSOL Multiphysics to
evaluate properties that depend on model variables such as temperature, pressure,
and composition.

Thermodynamics
To access the functionality for thermodynamic calculations, right-click the Global
Definitions node in the Model Builder tree and select Thermodynamics ( ). Using the

USING THERMODYNAMIC PROPERTIES | 297

 Reaction Engineering or Chemistry interfaces, Thermodynamics is also available on the
Reaction Engineering toolbar.

Figure 6-1: The Thermodynamics feature is available under Global Definitions.

Thermodynamic properties given as parameters or functions are collected in a so called

thermodynamic system. Each thermodynamic system includes a set of available species
and phases, as well as different models used for the thermodynamic property
calculations, for example an equation of state such as Peng-Robinson.

Select Thermodynamic System in the context menu to add a thermodynamic system

that uses the database included in the Chemical Reaction Engineering Module.

As an alternative, selecting External Thermodynamic System can make use of an

installed thermodynamics software to make the corresponding calculations.

It is also possible to import previously created and stored thermodynamic systems by

selecting Import Thermodynamic System (see Exporting and Importing
Thermodynamic Systems).

Use User Defined Species to add new species that are not available in COMSOL
database. You can also edit available species in the database.

298 | CHAPTER 6: THERMODYNAMICS

Figure 6-2: 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
may 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 | 299

 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.

The Thermodynamic System Wizard contains the following steps:

1 Select System
2 Select Species
3 Selecting a 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 elements in the
Name column. Click the Next button ( ) to proceed to the next step in the wizard.

Figure 6-3: Thermodynamic System Wizard: Select System.

SELECT SPECIES
Use the Species filter 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

300 | CHAPTER 6: THERMODYNAMICS

Add Selected button ( ) to add species to the Selected species table. Click the Next
button ( ) to proceed to the next step in the wizard.

Figure 6-4: Thermodynamic System Wizard: Select Species.

SELECTING A 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:

• Ideal Gas Law

• Peng-Robinson
• Peng-Robinson (Twu)
• Soave-Redlich-Kwong
• Soave-Redlich-Kwong (Graboski-Daubert)

USING THERMODYNAMIC PROPERTIES | 301

 When the package includes one or more liquid phases, the following additional models
are also available (in the Liquid phase model list):

• Ideal Solution
• Regular Solution
• Extended Regular Solution
• Wilson
• NRTL
• UNIQUAC
• UNIFAC

These models correspond to activity models.

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.

Use 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 following properties:

• Gas thermal conductivity

• Gas viscosity

For a single-phase liquid, or for a two-phase liquid-liquid system, there are models for
following properties:

• Liquid volume
• Gas-liquid surface tension
• Liquid thermal conductivity
• Liquid viscosity

302 | CHAPTER 6: THERMODYNAMICS

For systems with both vapor and liquid phases, all of the above properties are available.

Figure 6-5: 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.

USING THERMODYNAMIC PROPERTIES | 303

 SETTINGS
Selecting a Thermodynamic System node shows its Settings window with a description
of the package content and the available properties. Below follows a description of the
thermodynamic system settings.

Figure 6-6: Thermodynamic System Settings.

Provider:
Contains information about the thermodynamic system such as the version it was
created in and the manager used to create it. For a built-in thermodynamic system the
manager corresponds to COMSOL.

Species:
Lists the species included in the thermodynamic system. You can change the list of
species by adding or removing species in a thermodynamic system. For information on
how to change the list of species, see Add or Remove Species.

304 | CHAPTER 6: THERMODYNAMICS

Systems:
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 Properties:
Lists the parameters and function 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 reading, see
Species Property.

Mixture Properties:
Lists the available mixture property functions. Here you can see the mixture models
that are available. 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 Models:
When a liquid is present, use the Liquid phase model list to select the thermodynamic
model for the this phase.

When a gas is present, use the Gas phase model list to select the thermodynamic model
for this phase. If a liquid phase is also available and the Liquid phase model corresponds
to an equation of state, then the Gas phase model is set to the same model.

Property Models:
Displays the settings for the available individual property models. The property models
can be changed by selecting different values from the combo box in the Model
column. For example, for Gas thermal conductivity you can select Kinetic theory or Ideal
from the corresponding combo box. You can also select the property model in the last
step of the thermodynamic system wizard by selecting the Advanced option check box,
see Selecting a Thermodynamic Model.

Binary Interaction Parameter:

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 6-7
to edit the corresponding binary interaction parameter currently in use. In cases that

USING THERMODYNAMIC PROPERTIES | 305

 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 6-7: 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).

MODIFYING THE AVAILABLE SPECIES AND SYSTEM

It is possible to change 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, or from the context menu. When the

306 | CHAPTER 6: THERMODYNAMICS

properties of a User Defined Species has been changed, select Update From Species
for the changes to take effect in the thermodynamic system.

Figure 6-8: 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 ( ) 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 this coupling can be updated.

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.

USING THERMODYNAMIC PROPERTIES | 307

 Make sure to click the Finish button ( ) button in order for the changes to take
effect.

Note that changing the phase(s) in a thermodynamic system that is currently coupled
to a Reaction Engineering interface or a Chemistry interface breaks this coupling. See
the Coupling with the Reaction Engineering and the Chemistry Interfaces section for
how this coupling can be updated.

UPDATE FROM SPECIES

This option is available in a Thermodynamic System that includes a User Defined
Species. Use it to update the system following a change in the species properties.

WARNING INFORMATION
A sanity check is always performed when a Thermodynamic System is created. If any
problems are found, a Warning Information node listing the problems is added under
the package. One example when this occurs is when a parameter required for the
thermodynamic model, typically a binary interaction parameter, is not available in the
database.

External Thermodynamic Packages

The thermodynamics functionality includes support for creating properties from
external thermodynamic packages. In order to use external packages, the external
software has to be CAPE-OPEN compliant. The Chemical Reaction Engineering
Module supports the CAPE-OPEN Thermo 1.1 and the CAPE-OPEN Thermo 1.0
standards.

CAPE-OPEN is an open interface standard for chemical process simulation software

(Ref. 1). This standard defines rules and interfaces that allows linking between
compliant software. Some examples of CAPE-OPEN compliant software are:

• COCO/TEA (Free of charge package provider, Ref. 2).

• Multiflash™ (KBC Advanced Technologies plc).
• VMGThermo™ (Virtual Materials Group, Inc.).
• Simulis® Thermodynamics (ProsSim SA).
• Aspen Properties, aspenONE® (Aspen Technology, Inc.).
• COMThermo® packages (comes with Aspen HYSYS®).

308 | CHAPTER 6: THERMODYNAMICS

Accessing external thermodynamic systems allows species properties, mixture
properties, as well as phases equilibrium calculations (gas-vapor, liquid-liquid) to be
obtained from external software, such as the ones listed above.

INSTALLING EXTERNAL THERMODYNAMIC PACKAGES–AN EXAMPLE

TEA is a thermodynamics thermodynamic system that handles the physical and
thermodynamic property calculations for the simulation environment COCO. The
property data bank contains of over 190 commonly used chemicals, and the package
exhibits more than 100 property calculation routines with their analytical or numerical
derivatives. COCO is maintained by AmsterCHEM and is free to download from the
Internet (Ref. 2).

To use the external physical and thermodynamic property calculations from

COCO/TEA in COMSOL Multiphysics models, you need to go through the
following steps:

1 Download and install COCO, which includes the TEA thermodynamic system
manager. The software is available from
www.cocosimulator.org/index_download.html.
2 Create and configure a thermodynamic system template that handles physical and
thermodynamics calculations needed for your model. If you have already created a
package template earlier, or if an adequate thermodynamic system already exists in
the installation, this step is not needed.
3 Create an External Thermodynamic System node as detailed in the next section.
The installed packages are available in the Select Property Package step of the
Thermodynamic System Wizard.

External Thermodynamic System

The following assumes that you have installed external thermodynamic packages from
the properties of rm 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 6-2). Using a Reaction Engineering interface, you can also add an
external package by choosing External Thermodynamic System from the
Thermodynamics section of the Reaction Engineering toolbar.

USING THERMODYNAMIC PROPERTIES | 309

 SELECT PROPERTY PACKAGE
All installed packages, from providers such as COCO/TEA, Aspen Properties, etc, are
available in the Thermodynamic System Wizard (Figure 6-9). Select one of the packages
and click the Finish button ( ) in the upper right corner of the wizard in order to
add the package to 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.

Figure 6-9: 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.

Information about the selected package is displayed in the following sections.

310 | CHAPTER 6: THERMODYNAMICS

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.

Mixture Properties:
Lists the available functions that describe mixture properties. One example is the
density of a non-ideal mixture as a function of composition.

USING THERMODYNAMIC PROPERTIES | 311

 SETTINGS
Selecting the External Thermodynamic System node shows the thermodynamic system
settings with sections for available species, phases, species properties, and mixture
properties.

Figure 6-10: Settings seen when selecting an added External Thermodynamic System.

312 | CHAPTER 6: THERMODYNAMICS

 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.

Exporting and Importing Thermodynamic Systems

EXPORT THERMODYNAMIC SYSTEM

Right-click the Thermodynamic System node for the thermodynamic system that you
want to export (Figure 6-8) 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 6-2). Use the Select File window to navigate to a thermodynamic system file
and click Open.

Species Property
A Species Property is used to define and compute a pure species property. The available
properties consist of both parameters and functions. Some examples of available
parameters are molar mass, Lennard Jones diameter, and dipole moment. Some
examples of available functions are density, enthalpy, heat capacity, and viscosity. The
property functions created are either dependent on temperature alone, or both on
temperature and pressure. For all property functions, the first order derivative with
respect to temperature and, when applicable, with respect to pressure are automatically
defined.

Right-click the relevant Thermodynamic System node (see Figure 6-8), 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:

USING THERMODYNAMIC PROPERTIES | 313

 1 Select Properties
2 Select Phase
3 Select Species
4 Species Property Overview

SELECT PROPERTIES
First use the Amount base unit list to define the base unit. Select mol or kg.

Use the filter to search among the available properties. Select one or more properties
in the list and click the Add Selected button ( ) to add them to the Selected properties
list.

Click the Next button ( ) to proceed to the next step, selecting the species.

Figure 6-11: Species Property Wizard; Select Properties.

314 | CHAPTER 6: THERMODYNAMICS

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 6-12: Species Property Wizard; Select Phase.

Note that for parameters (constants) this step is skipped.

SELECT SPECIES
Select one or more of the species available in the thermodynamic system and use the
Add Selected button ( ) to add them to the Selected species table. One property
function is created for each of the selected species.

Click the Next button ( ) to proceed to the next step in the wizard, which is selecting
the phase for the property.

Figure 6-13: Species Property Wizard; Select Species

USING THERMODYNAMIC PROPERTIES | 315

 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 it and select Species Property to
start the Species Property Wizard.

Figure 6-14: Create a Species Property from an existing species node.

316 | CHAPTER 6: THERMODYNAMICS

SETTINGS
Selecting a Species Property node shows the settings for such property.

Figure 6-15: 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.

USING THERMODYNAMIC PROPERTIES | 317

 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.

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 6-16: Show constant and temperature dependent properties references for species
functions.

318 | CHAPTER 6: THERMODYNAMICS

The reference for the constant or temperature dependent property is available in the
Comments field in the Node Properties section.

Figure 6-17: Properties window for species function.

Mixture Property
A Mixture Property is used to compute a property function that depends on the
concentration of the species in a thermodynamic system. Some examples of the
available property functions are density, enthalpy, heat capacity, and surface tension.

Apart from the composition, the mixture property functions are also dependent on
temperature and pressure. The first order derivatives with respect to temperature and
pressure are automatically defined.

Right-click the relevant Thermodynamic System node (see Figure 6-8), 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

USING THERMODYNAMIC PROPERTIES | 319

 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 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.

MIXTURE PROPERTY OVERVIEW

The final step of the wizard displays an overview of the parameters and functions that
are added by the wizard. 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.

320 | CHAPTER 6: THERMODYNAMICS

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
it and select Mixture Property to start the Mixture Property Wizard.

Figure 6-18: Mixture properties can be created by right-clicking a Mixture node under a
thermodynamic system.

by right-click and select Mixture Property in the menu.

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 to
be described in a model is a distillation process, where a multiphase feed stream is
separated into a vapor and a liquid product and where the concentrations of the species
in each phase are required. Equilibrium calculations involve combining the

USING THERMODYNAMIC PROPERTIES | 321

 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. The Chemical Reaction
Engineering Module can handle all of the above cases using the equilibrium calculation
functionality. Phase envelopes, bubble point, and dew point can be calculated for any
number of species.

Right-click the relevant Thermodynamic System node (see Figure 6-8), or the relevant
External Thermodynamic System node, and select Equilibrium Calculation to start the
Equilibrium Calculation Wizard.

The Equilibrium Calculation Wizard consists of the following steps:

1 Select species
2 Equilibrium Specifications
3 Equilibrium Function Overview

The Equilibrium Calculation settings include three types of equilibrium functions.

• The first function type is used to detect whether a phase is present in the system and
includes “exist” in its name.
• The amount function computes the total amount of material in each phase.
• The phase composition functions compute the mass or mole fraction of each species
in each phase, depending on the selected base unit for the equilibrium calculation.

SELECT SPECIES
Select one or more of the species available in the thermodynamic system and use the
Add Selected button ( ) to add them to the Selected species table. Click the Next
button ( ) to proceed to the next step in the wizard.

322 | CHAPTER 6: THERMODYNAMICS

EQUILIBRIUM SPECIFICATIONS
Use the Amount base unit list to use either kg or mol as base unit.

Select two Equilibrium conditions that define the current equilibrium, for example a
given pressure and a temperature. These equilibrium conditions are used as arguments
in the equilibrium functions, in addition to the composition (overall fractions of
species).

The available equilibrium conditions are: Temperature, Pressure, Phase fraction, Energy
(or Energy of formation), Enthalpy (or Enthalpy of formation), Specific volume, and
Entropy (or Entropy of formation). For chemical reactions, it is recommended to use
Enthalpy of formation, Entropy of formation and Energy of formation, since they account
for heat of reactions.

Figure 6-19: Equilibrium Calculation Wizard; Equilibrium Specifications.

Selecting Phase fraction as one of the equilibrium conditions activates the Solution type
input field. This can be used to indicate the direction of the desired solution, which is
of great use especially near critical points. The options Undefined, Normal, or Retrograde
define different directions for the search of the solution to the equilibrium equations.
Using Normal means that the derivative of the vapor phase fraction with respect to
temperature (at constant pressure and composition) is kept positive and the derivative
of the vapor phase fraction with respect to pressure (at constant temperature and

USING THERMODYNAMIC PROPERTIES | 323

 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 phenomena is known as retrograde
condensation. This means that under isothermal conditions, when the pressure
decreases, some of the vapor condenses into liquid instead of expanding or vaporizing.
An example of such system is formation of liquid hydrocarbons in a gas reservoir as the
pressure decreases below the dew point pressure. In this case, setting Solution type to
Normal or Retrograde may not be sufficient to distinguish between the two solutions.

Note that the Solution type setting is only available for a built-in thermodynamic
systems. For external thermodynamic systems, the corresponding functionality needs
to be supplied by the thermodynamic software provider. For instance, the
COCO/TEA provider does not support the Normal or Retrograde options. In those
cases, the Solution type should be Undefined.

Click the Next button ( ) to proceed to the next step.

EQUILIBRIUM FUNCTION OVERVIEW

In this step, you can review all the functions including units and arguments. Click the
Finish button ( ) to exit the wizard and add functions at equilibrium state to the
current thermodynamic system.

THE EQUILIBRIUM CALCULATION NODE

When creating an Equilibrium Calculation, the resulting functions are collected under
the Mixture node. You can create new functions from an existing Mixture node.
Right-click it and select Equilibrium Calculation to start the Equilibrium Calculation
Wizard (see Figure 6-18).

SETTINGS
Selecting an Equilibrium Calculation node displays the settings including the property
functions, see Figure 6-20.

324 | CHAPTER 6: THERMODYNAMICS

Plot Parameters:
Can be used to evaluate and plot the equilibrium function for a range of argument
values. First specify which of the included functions to plot. Then apply a Lower limit
and Upper limit for each argument and click the Plot button ( ).

Figure 6-20: Settings window; Equilibrium calculation.

USING THERMODYNAMIC PROPERTIES | 325

 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 automatically created by
coupling to an existing Thermodynamic System under Thermodynamics.

Examples of species properties that can be automatically created are the molar mass,
the heat capacity, the enthalpy, and the entropy of each species. Parameters and
functions for these properties are created by the package. 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.

Note that using a thermodynamic system significantly increases the modeling

capabilities in the Reaction Engineering and Chemistry interfaces. All ideal and non-ideal
thermodynamic models, for gases and liquids, are directly available and also
automatically updated by editing the settings for the used thermodynamic system. The
Chemistry interface can furthermore be used to make the mixture properties readily
available in space dependent models for modeling of mass transport, heat transfer, or
fluid flow.

REACTION ENGINEERING

Mixture Properties
You can couple a Reaction Engineering interface with an existing thermodynamic
system in the Reaction Engineering interface’s settings window.

You need to have at least one species defined in the Reaction Engineering interface in
order to couple to a thermodynamic system. You can make this coupling in settings
window for the Reaction Engineering interface by selecting the Thermodynamics check
box in the Mixture Properties section.

326 | CHAPTER 6: THERMODYNAMICS

Select a thermodynamic system from the Property package list. Use the Phase list to
select the phase to be used in the Reaction Engineering interface.

Figure 6-21: 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
ensures that the arguments in the thermodynamic system functions are correctly
defined.

Use the drop-down lists in the From Thermodynamics column to match each species in
the interface to a species in the coupled thermodynamic system.

For each species matched, the required property parameters and functions are added
under to the corresponding thermodynamic system.

When all species are matched, the interface is considered fully coupled and functions
representing mixture properties, such as density, are also added automatically under
the corresponding thermodynamic system.

Figure 6-22: Matching the species in Reaction Engineering to those in the corresponding
thermodynamic system.

USING THERMODYNAMIC PROPERTIES | 327

 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 drop-down list, see below.

Figure 6-23: Select Calculate mixture properties when coupled to a thermodynamic system.

CHEMISTRY

Mixture Properties
Coupling a Chemistry interface to a Thermodynamic System is initiated by selecting the
Thermodynamics check box, in the same way as for the Reaction Engineering interface
above.

Species Matching
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.

The Chemistry interface is coupled to a thermodynamic system by selecting

Thermodynamics in the Mixture Properties section, analogous to the Reaction
Engineering interface above. 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 drop-down 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.

328 | CHAPTER 6: THERMODYNAMICS

When all species are matched, the interface is fully coupled and functions representing
mixture properties, such as the density, are added automatically under the
thermodynamic system coupled to.

Figure 6-24: Matching concentration variables in a Chemistry interface, as well as species

in a coupled Thermodynamic System.

Calculate Thermodynamic Properties

When Calculate mixture properties is selected, property functions for the mixture
properties are created automatically by the thermodynamic system when species
matching is complete. For each property defined by the coupled package,
Thermodynamics is selected by default in the corresponding property’s drop-down list.

MIXTURE PROPERTY DEFINITIONS WHEN COUPLING TO

THERMODYNAMICS
When all species in a physics interface are matched to corresponding species in a
thermodynamic system, the mixture properties are calculated based on the
composition of the mixture. For example, consider Zmix(T, P, n1, ..., nm), which
denotes a generic extensive mixture property for a mixture of m number of species.
The property function’s arguments are temperature T, pressure P, and the number of
moles, n, for each species.

When the system is fully matched, the mixture property Zmix is defined as:

USING THERMODYNAMIC PROPERTIES | 329

 m
Z mix =  ni Zi (6-1)
i=1

where Zi is the partial molar of species i:

∂Z mix ( T, P, n 1, n 2, …, n m )
Z i =  ----------------------------------------------------------------------- (6-2)
 ∂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 ) = (6-3)

 ∂Z mix ( T, P, x 1, …, x m )
Z +  ------------------------------------------------------------
 mix ( T, P, x 1, …, x m )  ∂xi T, P, x i

m ∂Z mix ( T, P, x 1, …, x m ) 
–   xi  -----------------------------------------------------------
∂xi
- 
 T, P, x  
i=1
i


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 =  n i Z i ( T, P ) (6-4)
i=1

using the pure species properties Zi =Zmix(T, P, xi =1,0,...,0).

Evaluating a Property Function in a Physics Interface

The functions set up using a thermodynamics thermodynamic system 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 6-25 shows the Reaction
Engineering interface from the Application Library example Hydrodealkylation in a
Membrane Reactor. In this example, the Species Thermodynamic Expressions section
requires input for the molar entropy, the enthalpy and the heat capacity of benzene.

330 | CHAPTER 6: THERMODYNAMICS

These functions, generated using an external thermodynamic system, have been
entered in the corresponding input fields using the appropriate arguments.

Figure 6-25: The enthalpy and heat capacity of benzene are evaluated using external
property calculations through a thermodynamics package. In this case, the functions are
temperature 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. It can also be used to edit a databases 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, together with predefined database species as well as
other user defined species.

The data needed for a user defined species includes both material properties, such as
the molar mass and the vapor pressure, and properties for specific thermodynamic
models or transport models (see Thermodynamic Models and Theory). For instance,
in order to use the UNIFAC Thermodynamic model, you need to define UNIFAC
groups for the new species.

Note that the thermodynamics calculator includes measures to handle missing species
properties, sometimes by applying approximations. For instance, if the Wilson volume
is not available, the liquid volume at normal boiling point is used instead. If data for
this is also missing, it is estimated from the saturated liquid density correlation.

When creating a user defined species it is recommended to add the following common
material properties:

• Molecular mass

USING THERMODYNAMIC PROPERTIES | 331

 • Critical properties
• Acentric factor
• Absolute entropy
• Standard enthalpy of formation
• Molecular mass
• 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, choose User Defined Species from the
Thermodynamics section of the Reaction Engineering toolbar.

The User Defined Species Wizard contains the following steps:

1 Enter Name and Formula

2 Enter Parameters
3 Define Properties

332 | CHAPTER 6: THERMODYNAMICS

ENTER NAME AND FORMULA
Enter the Name, CAS number, and the Chemical formula for the new species.

Figure 6-26: 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 6-27: 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.

USING THERMODYNAMIC PROPERTIES | 333

 ENTER PARAMETERS
Define the necessary parameter for the new species.

Constants
Use this table to define material constants such as molar mass, critical temperature, and
standard enthalpy of formation.

Figure 6-28: User Defined Species Wizard; Enter material constants.

334 | CHAPTER 6: THERMODYNAMICS

Structure information
If you want to use the UNIFAC model, specify the structure formula, the UNIFAC
groups and their number occurrences.

Figure 6-29: User Defined Species Wizard; Specify the structure information in the Enter
Parameters step.

Model parameters
Specify the parameters for the thermodynamic models and transport models in use.

Figure 6-30: 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

USING THERMODYNAMIC PROPERTIES | 335

 2 3
f ( T ) = a0 + a1 T + a2 T + a3 T (6-5)

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).

336 | CHAPTER 6: THERMODYNAMICS

Click the Finish button ( ) in the top of the Settings window to finalize the species
and add it to the User Defined Species node under Thermodynamics.

Figure 6-31: 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

USING THERMODYNAMIC PROPERTIES | 337

 sections as seen in Figure 6-32 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).

Figure 6-32: The Settings widow for a User Defined Species.

338 | CHAPTER 6: THERMODYNAMICS

References
1. www.colan.org

2. Cape Open to Cape Open Simulation Environment,

www.cocosimulator.org/index_download.html

USING THERMODYNAMIC PROPERTIES | 339

 Thermodynamic Models and Theory
In this section:

• Introduction
• Thermodynamic Models
• Selecting the Right Thermodynamic Model
• 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 ) (6-6)
RT

340 | CHAPTER 6: 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 comparisons of different
cubic EOS can be found in Ref. 4–Ref. 5.

The equation of state models available in the thermodynamic properties database are:

• Ideal Gas Law

• Peng-Robinson
• Peng-Robinson (Twu)
• Soave-Redlich-Kwong
• Soave-Redlich-Kwong (Graboski-Daubert)

Ideal Gas Law

The ideal gas law equation of state is

RT
P = -------- (6-7)
V

As the name suggests, the ideal gas law is only applicable to gases. In fact, its use is
limited to gases at low to moderate pressures.

Peng-Robinson
The classical Peng-Robinson (PR) equation of state Ref. 7 is given by

RT aα
P = ------------- – ------------------------------------
- (6-8)
V – b V 2 + 2bV – b 2

where for species i,

2 2
R Tc
a i = Ω A -------------- (6-9)
Pc

RT c
b i = Ω B ----------- (6-10)
Pc

1 1
Ω A = --- + --- Ω B ( 4 + 10Ω B ) (6-11)
3 3

Ω B =  β – ----------------- – 0.03125
63
(6-12)
1024β

THERMODYNAMIC MODELS AND THEORY | 341

 The alpha function, αi, is given by

2
α i = [ 1 + ( 0.37464 +1.54226ω i – 0.26992ω i2 ) ( 1 – T r, i ) ] (6-13)

For mixtures

  xi xj ( 1 – kPR,i,j )
aα = ( aα ) i ( aα ) j (6-14)
i j

 xi bi
b = (6-15)
i

The binary interaction parameters (BIPs), kPR, are symmetric with zeros in the
diagonal:

k PR = k PR,i,j (6-16)

k PR,i,j = 0 (6-17)

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 modificationRef. 8 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 ) ) (6-18)

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.

Soave-Redlich-Kwong
The classical Soave-Redlich-Kwong equation of state Ref. 9 is given by

RT aα
P = ------------- – ----------------------- (6-19)
V – b V(V + b)

with

342 | CHAPTER 6: THERMODYNAMICS

 1
α = -------- (6-20)
T

and for the pure species i,

2 2.5
R Tc
a i = Ω A ------------------ (6-21)
Pc

RT c
b i = Ω B ----------- (6-22)
Pc

1 1
Ω A = --- + --- Ω B ( 3 + 3Ω B ) (6-23)
3 3

1-
-- --2-
1 3 3 1
Ω B = ------ 2 27 – --- (6-24)
27 3

For mixtures

  xi xj ( 1 – kSRK,i,j )
a = ai aj (6-25)
i j

 xi bi
b = (6-26)
i

The binary interaction parameters, kSRK, are symmetric with zero in the diagonal:

k SRK ,i,j = k SRK ,j,i (6-27)

k SRK ,i,j = 0 (6-28)

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 state
is a version of Equation 6-19 modified by Soave Ref. 10, 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 ) ] (6-29)

THERMODYNAMIC MODELS AND THEORY | 343

 Soave-Redlich-Kwong (Graboski-Daubert)
The Graboski and Daubert Ref. 11 modification of the Soave-Redlich-Kwong
equation of state replaces alpha function by

2
α i = [ 1 + ( 0.48508 +1.55174ω i – 0.1561ω i2 ) ( 1 – T r, i ) ] (6-30)

except for H2, where it is replaced by

α H2 = 1.202 exp ( – 0.30228T r, H2 ) (6-31)

LIQUID PHASE MODELS

Activity coefficient models

Activity coefficient models are used to describe liquid mixtures at low to moderate
pressure and temperature but where equations of state are inadequate. When using
activity coefficient models, the partial fugacity for species i in the liquid phase is defined
as

f̂ i, l = x i γ i φ i, sat P i, sat F i (6-32)

which yields

P i, sat
φ̂ i, l = γ i φ i, sat --------------- F i (6-33)
P

where the activity coefficient, γi, describes the non-ideal 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
---------
RT 
dp (6-34)

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 ) (6-35)
RT

The Poynting correction can often be ignored for moderate pressure. Hence,
Equation 6-33 can be expressed as

344 | CHAPTER 6: THERMODYNAMICS

 P i, sat
φ̂ i, l = γ i φ i, sat --------------- (6-36)
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 --------------- (6-37)
P

This reduction can be selected explicitly in case the vapor phase is not ideal.

The logarithmic transformation of Equation 6-33 is:

ln φ̂ i, l = ln γ i + ln φ i, sat + ln P i, sat – ln P + ln F i (6-38)

Ideal Solution
For an ideal solution the activity coefficient is equal to one, which gives:

ln γ i = 0 (6-39)

Regular Solution
The Scatchard-Hilderbrand equation Ref. 13 for non-polar mixture is

2
V i ( δ i – δ av )
ln γ i = --------------------------------- (6-40)
RT

where Vi is species molar volume and δi is species solubility parameter, and δav is

 ( xi Vi δi ) (6-41)
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 ≡ --------------------
- (6-42)
V i, l, b

THERMODYNAMIC MODELS AND THEORY | 345

 Extended Regular Solution
The extended Scatchard-Hildebrand equation adds the Flory and Huggins correction
to the regular solution model Ref. 15:

2
V i ( δ i – δ av )
ln γ i = --------------------------------- + ln ( θ i ) + 1 – θ i (6-43)
RT

where

Vi
θ i = ----------------------- (6-44)
 ( xi Vi )
i

Wilson
Wilson Ref. 16 derived his activity coefficient model from a consideration of
probabilities of neighboring molecules in a liquid

 
 xΛ    (6-45)
 -----------------------
j j, i 
ln γ i = 1 –  
- – ln 
   xj Λi, j
j
 
 x k Λ j, k

j
k

V w, j λ i, j
Λ i, j = ----------- exp  – -------- (6-46)
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 non-symmetric and
with zeros in its diagonal. All off-diagonal values must be specified

λ i, i = 0 (6-47)

Λ i, i = 1 (6-48)

NRTL
Renon and Prausnitz (Ref. 17) formulated a three parameter activity coefficient model
that is able to describe liquid-liquid equilibrium; the non-random two-liquid (NRTL)
model:

346 | CHAPTER 6: THERMODYNAMICS

   
 x j τ j, i G j, i 
 x j G j, i 
  x k τ k, j G k, j 
 (6-49)

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 = --------- (6-50)
T

G i, j = exp ( – α i, j τ i, j ) (6-51)

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 (6-52)
T

G i, j = exp ( β i, j – α i, j τ i, j ) (6-53)

The binary interaction parameters, Ai,j, are specified in terms of absolute temperature.
The diagonal values are zero and the matrix is non-symmetric. All off-diagonal values
must be specified.

The binary interaction parameters, Bi,j, have values of zero on the diagonal and the
matrix is non-symmetric. 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 non-symmetric. 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 (6-54)

B i, i = 0 (6-55)

α i, i = 0 (6-56)

α j, i = α i, j (6-57)

THERMODYNAMIC MODELS AND THEORY | 347

 τ i, i = 0 (6-58)

G i, i = 1 (6-59)

β i, i = 0 (6-60)

UNIQUAC
Abrams and Prausnitz followed up with another two-liquid model known as Universal
Quasi Chemical equation (UNIQUAC) Ref. 18 which is formulated in terms of two
activity coefficients:

ln γ i = ln γ i, comb + ln γ i, res (6-61)

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
(6-62)
2  θi  θ i 

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  -------------------------
 
- –
 --------------------------- (6-63)
 x j q j  x j q j τ k, j



 j 
j  
k

where

ri
φ i = ----------------- (6-64)
 xj rj
j

qi
θ i = ----------------- (6-65)
 xj qj
j

– Δ E i, j
τ i, j = exp  ----------------- (6-66)
 T 

348 | CHAPTER 6: THERMODYNAMICS

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 (6-67)

τ i, i = 1 (6-68)

The volume parameters, ri and surface area parameters, qi are model-specific

parameters for each species. If the parameters are not specified then they can be derived
from the van der Waals volume, VVDW,i, and area, AVDW,i, respectively

V VDW, i
r i = -----------------------------------
–3
- (6-69)
0.01517 ×10

A VDW, i
q i = -------------------5- (6-70)
2.5 ×10

For all species ri or VVDW,i and qi or AVDW,i must be specified.

UNIFAC
The UNIQUAC Functional-group Activity Coefficients (UNIFAC; see Ref. 19) 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 6-61. The
combinatorial part follows from equation Equation 6-62, where

ri =  ν k, i r k (6-71)
k

qi =  ν k, i q k (6-72)
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 6-61 is calculated
from a summation over functional groups:

ln γ i, res =  νk, i ( ln γk, res – ln γi, k, res ) (6-73)

k

THERMODYNAMIC MODELS AND THEORY | 349

 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  --------------------------
 
- –
 ----------------------------- (6-74)
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 = ----------------------------------- (6-75)
 
 
 x i ν k, i
 
i k

For the calculation of a pure species’ i residual activity we get:

ν m, i
x m = ----------------- (6-76)
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  – ------------- (6-77)
 T 

The binary interaction parameters, Ak,m, are specified in terms of absolute

temperature. The diagonal values are zero, the matrix is non-symmetric. All
off-diagonal values must be specified.

The default group and interaction parameters are those published by the UNIFAC
consortium (Ref. 20 through Ref. 25), with added groups from Balslev and Abildskov
(Ref. 26) 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.

350 | CHAPTER 6: THERMODYNAMICS

Chao Seader (Grayson-Streed)
The Chao-Seader model Ref. 12 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 (6-78)

The activity is based on the Scatchard-Hildebrand equation Ref. 13 and presented in

Equation 6-40 to Equation 6-42. 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 6-75, 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 (6-79)

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 (6-80)
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 ) (6-81)
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. 14 and given in Table 6-1.
TABLE 6-1: CHAO-SEADER GRAYSON-STREED FUGACITY COEFFICIENT PARAMETERS

H2 CH4 OTHER ALL

Ai,0 1.50709 1.36822 2.05135 Ai,10 -4.23893

Ai,1 2.74283 -1.54831 -2.10899 Ai,11 8.65808
Ai,2 -0.02110 Ai,12 -1.22060
Ai,3 0.00011 0.02889 -0.19396 Ai,13 -3.15224

THERMODYNAMIC MODELS AND THEORY | 351

 TABLE 6-1: CHAO-SEADER GRAYSON-STREED FUGACITY COEFFICIENT PARAMETERS

H2 CH4 OTHER ALL

Ai,4 -0.01076 0.02282 Ai,14 -0.02500

Ai,5 0.008585 0.10486 0.08852
Ai,6 -0.02529
Ai,7 -0.00872
Ai,8 -0.00353
Ai,9 0.00203
The corresponding vapor phase model is Redlich-Kwong equation of state. The
Chao-Seader (Grayson-Streed) model is valid when

- 255 K < T < 533 K

- P < 6.89 MPa
- Pr < 0.8
- 0.5 < Tr,i < 1.3, for all hydrocarbons except CH4
- xCH4 < 0.3
- For system that includes CH4 or H2S:

 xi Tr, i < 0.93

i

The enthalpy, entropy and Gibbs free energy can be calculated from Equation 6-104
to Equation 6-113.

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 = ------ (6-82)
Vl

Equation of State
When an equation of state is selected as the thermodynamic model, the liquid volume
is calculated using the equation of state model. In the other cases, when the
thermodynamic model is not an equation of state, an equation of state can be explicitly
selected to calculate the liquid volume.

352 | CHAPTER 6: THERMODYNAMICS

Note, when defining the equation of state for vapor and liquid systems, both phases
must use the same equation of state.

Ideal Mixture
For an ideal mixture the liquid volume is computed from the pure species densities:

xi
V l, m =  --------
ρ i, l
(6-83)
i

The pure species densities are evaluated from the built-in database.

COSTALD
Hankinson and Thomson Ref. 27 presented the Corresponding States Liquid Density
(COSTALD) equation as

V -
------------ = V r, ref ( 1 – ωV r, δ ) (6-84)
V mix

V r, ref = 1 + a ( 1 – T r ) 1 / 3 + b ( 1 – T r ) 2 / 3 + c ( 1 – T r ) + d ( 1 – T r ) 4 / 3 (6-85)

e + fT r + gT r2 + hT r3
V r, δ = ---------------------------------------------------- (6-86)
T r – 1.00001

1   
V mix = --- 
4  xi Vi + 3   xi Vi2 / 3   xi Vi1 / 3  (6-87)
i i i

 2
 
 x i T c, i V i

i
T c = ------------------------------------------ (6-88)
V mix

 -----
T
 T- T < Tc
Tr =  c (6-89)
1 T ≥ Tc


ω =  xi ωi (6-90)
i

THERMODYNAMIC MODELS AND THEORY | 353

 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 (6-91)
,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 (6-92)

If the COSTALD acentric factor, ωi is not specified then it can be set equal to the
generic acentric factor for species i. Critical temperature, Tc,i must be specified for all
species.

The correlation parameter values are:

TABLE 6-2: REDUCED VOLUME CORRELATION PARAMETERS IN COSTALD

a -1.52816 e -0.296123
b 1.43907 f 0.386914
c -0.81446 g -0.0427258
d 0.190454 h -0.0480645

Rackett
The Rackett equation Ref. 28 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 (6-93)
i i i

 xi Tc, i
Tc = (6-94)
i

 -----
T
 T- T < Tc
Tr =  c (6-95)
1 T ≥ Tc


354 | CHAPTER 6: THERMODYNAMICS

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 (6-96)

Selecting the Right Thermodynamic Model

There are methods to choose the appropriate thermodynamic models, see Ref. 49.
This choice depends on the nature of the property, composition of the mixture,
operational pressure and temperature, and availability of model’s parameters for the
simulation, see Ref. 50. Below is a decision tree that can be used as a guide for
choosing the thermodynamic model:

Figure 6-33: Decision tree to select thermodynamics model.

It is possible to modify the database species properties such as parameters and

temperature-dependent function for a thermodynamic system thermodynamic system.

THERMODYNAMIC MODELS AND THEORY | 355

 In the same manner, you can add new species that do not exist in the database. To do
this, right click on the Property package in the Model builder and select Export
thermodynamic system. Save the thermodynamic system as an xml file.

All the parameters and temperature-dependent properties are saved inside

<Compound></Compound> command phrase. For example to edit the acentric factor of
methane from 0.01141 to 0.2; open the thermodynamic system file, under compound
methane and change the value for acentric factor as <AcentricFactor
>0.2</AcentricFactor>.

For temperature dependent-functions for example liquid Density, the section appears
as

<Density>
<Phase>Liquid</Phase>
<Coefficients>Tlb;a0;a1;a2;a3;Tub</Coefficients>
<Data>Tlb;f(Tlb);Tub;f(Tub)</Data>
<Comment></Comment>
</Density>

where Tlb and Tub are lower and upper bound for temperature. The a1 to a4 are
coefficients for a cubic polynomial as f(T) = a0 + a1*T+ a2*T2+ a3*T3 fitted to the
experimental data. The unit for temperature is K, See Table 6-3 for other units:
TABLE 6-3: UNIT FOR TEMPERATURE DEPENDENT PROPERTIES

PROPERTY UNIT
3
liquid density mol/m
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

Database includes all the references for constant and temperature dependent
properties. In the saved thermodynamic system, it is located between
<Comment></Comment>. Alternatively under the Thermodynamic System node, you
can right click on the created species function created and select Properties.

356 | CHAPTER 6: THERMODYNAMICS

Thermodynamic Properties Definitions
The thermodynamic properties provided are listed as species and mixture property in
a Property package.

Ideal Gas
The ideal gas law is independent of composition and determines V at given T and P.
Density can be calculated from

1
ρ = ---- (6-97)
V

The partial fugacity coefficients

ln φ̂ i = 0 (6-98)

The ideal gas enthalpy for mixture

 T 
 xi  Hi, ig, T T
H ig = + C P, i, ig dT (6-99)
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 =  x i  S i, ig, T ref – R ln x i +
 T ref
-----------------
T   P ref
- (6-100)
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 (6-101)

Equation of State
The equation of state determines V at given x, T, and P. Density can be expressed as
Equation 6-97. The partial fugacity coefficients are derived from

P
ˆ
0  Vi – --------
1 RT
ln φ̂ i = -------- (6-102)
RT P

THERMODYNAMIC MODELS AND THEORY | 357

 where Vi is the partial molar volume. The enthalpy, entropy, and Gibbs free energy
follow from the partial fugacity coefficients and the ideal gas contributions as:

∂ ln φ̂ i
H = H ig – RT 2  xi  -------------
∂T 
- (6-103)
i

∂ ln φ̂ i
S = S ig – R  xi  ln φ̂i + T -------------
∂T 
- (6-104)
i

G = G ig – RT  xi ln φ̂i (6-105)
i

Heat Capacity

Heat capacity at constant pressure is calculated from

∂H
C P =  -------- (6-106)
 ∂T  P,x

It is available when enthalpy is available. Heat capacity at constant volume is defined by

∂H
C v =  -------- (6-107)
 ∂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  -------  ------- (6-108)
 ∂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 (6-109)
 ∂T P,x  ∂P T,x

Rearranging equations above gives

∂V
T  -------
 ∂T P,x
C v = C P + ------------------------ (6-110)
 ∂V
-------
 ∂P T,x

358 | CHAPTER 6: THERMODYNAMICS

Cv is available if Cp and volume are available and fluid is compressible by means of
volume is pressure dependent. For ideal gas Equation 6-108 express as

Cp – Cv = R (6-111)

Specific heat capacity ratio is defined as

Cp
ϒ = ------- (6-112)
Cv

Activity Coefficient Models

The enthalpy, entropy, and Gibbs free energy follow from the activity coefficients and
the ideal gas contributions in Equation 6-99 – Equation 6-101. 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
(6-113)
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 
- (6-114)
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 =  x i  H i, ig, T ref +
 T ref
C P, i, ig dT – T  S i, ig, T ref +

(6-115)
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

THERMODYNAMIC MODELS AND THEORY | 359

 fˆi = x i φ̂ i P (6-116)

Internal energy is calculated from

 xi Ui, ig, ref

U = H – PV + (6-117)
i

where Ui,ig,ref is the enthalpy of an ideal gas to the species enthalpy at the selected
reference state.

K-values for phases p and q are taken from

φ̂ i, q
K i, p, q = --------- (6-118)
φ̂ i, p

If only liquid phases are defined, the K-value calculation is reduced to

γ i, q
K i, p, q = --------- (6-119)
γ i, p

 xi Mi
M mix = (6-120)
i

Standard Enthalpy of Formation and Absolute Entropy terms

Formation terms are not included in the enthalpy, entropy, or the internal energy. If
the enthalpy of formation is specified for all species, EnthalpyF (HF) represent the
enthalpy including the formation terms. If the absolute entropy of all species are
specified then the EntropyF (SF) includes the absolute entropy.

At reference conditions, the heat of any reaction relates to the heat of formation as

ΔH reac, ref =  νi ( ΔHf, ref ) (6-121)

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 (6-122)

i

360 | CHAPTER 6: 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

 xi Sabs, i
SF = S + (6-123)
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 COMSOLThermoDB are not included entropy of formation of species,
entropy Equation 6-123 and in consequence Gibbs free energy Equation 6-105 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 (6-124)
j

where the entropy of formation of species i is calculated from its elemental constituent
j. For example, entropy of formation of ammonia at 298K is

N 2 ( g ) + 3H 2 ( g ) ⇔ 2NH 3 (6-125)

ΔS f, NH3 = 2S abs, NH 3 – ( S abs, N 2 + 3S abs, H 2 ) (6-126)

The values from RHS of Equation 6-126 can be extracted from

COMSOLThermoDB. This value should be used in Equation 6-122 to estimate the
absolute value of Gibbs free energy of species.

THERMODYNAMIC MODELS AND THEORY | 361

 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 a variety of models that are available in the thermodynamic
database for thermal conductivity and viscosity as described below:

• Vapor Thermal Conductivity

• Vapor Viscosity
• Liquid Thermal Conductivity
• Liquid Viscosity

VAPOR THERMAL CONDUCTIVITY

Ideal
The thermal conductivity correlations is according to:

 x i λ i , v + Δλ v , P
λv = (6-127)
i

The pressure correction Δλv,P is calculated from the method of Stiel and Thodos, see
Ref. 29, 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 ) ) (6-128)
MT c1 / 6 Z c5

362 | CHAPTER 6: THERMODYNAMICS

 ρ
ρ r = ----- (6-129)
ρc

1
ρ c = ------ (6-130)
Vc

The mixing rules are as suggested by Yorizane, see Ref. 30:

 xi  xj Vc, i, j
Vc = (6-131)
i j

 xi  xj Vc, i, j Tc, i, j (6-132)

i j
T c = -----------------------------------------------------
-
Vc

 xi ωi
ω = (6-133)
i

Z c = 0.291 – 0.08ω (6-134)

RT c Z c
P c = ----------------- (6-135)
Vc

 xi Mi
M = (6-136)
i

where the binary constants are

1
V c, i, j = --- ( V c1, /i3 + V c1,/j3 ) 3 (6-137)
8

T c, i, j = T c, i T c, j (6-138)

The Stiel and Thodos coefficients are

TABLE 6-4: PRESSURE CORRECTION PARAMETERS

A B C
ρr < 0.5 A1=2.702×108 B1=0.535 C1=-1
0.5 ≤ ρr < 2.0 A =2.528×108
2 B2=0.670 C2=-1.069
ρr ≥ 2.0 A3=0.574×108 B3=1.155 C3= 2.016

THERMODYNAMIC MODELS AND THEORY | 363

 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 = – ------------------------------------------------------------------------------------------------------------------------------- (6-139)
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 = – ------------------------------------------------------------------------------------------------------------------------------- (6-140)
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. 31) provided an equation for the interaction parameters
of the method of Wassiljewa (see Ref. 32) based on the kinetic theory, to provide
mixture thermal conductivity from pure species values

 
 xλ  (6-141)
 ------------------------
i i, v 
λv =  
- + Δλ v, P

i
 
 x j λφ i, j

j

2
 T + 3   
 --- T b, i   9
 T +  --4- T b, i T b, j
η M 3 / 4  2  
= ---  1 + ----------  -------  ------------------------------   ----------------------------------------------
1 i, v j
φ i, j (6-142)
4 η j, v  M i    
T +  --- T b, j   T +  --- T b, i 
3 3
 
 2    2  

where the pressure correction Δλv,P is calculated from Equation 6-130. 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.

364 | CHAPTER 6: THERMODYNAMICS

VAPOR VISCOSITY

Wilke
Wilke, see Ref. 33, based his method for mixture viscosity of the vapor phase on kinetic
theory:

 
 xη  (6-143)
 ----------------------
,

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 = ------------------------------------------------------ (6-144)
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. 34) uses the same basic equation as Wilke (Equation 6-143).
However, Equation 6-144 is replaced by

η i, v
ψ i, j = S i, j A i, j ---------
- (6-145)
η j, v

and the interaction parameter is defined as

 
β i, j  RM i, j – RM i0.45 ,j


A i, j = -------------------- 1 + ----------------------------------------------------------------------------------------- (6-146)
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 = ------- (6-147)
 ( 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. 35)

THERMODYNAMIC MODELS AND THEORY | 365

 Stockmayer’s polar parameter δs,i(Ref. 36 - Ref. 37) 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 = ---------------------------------------------------------------------------- (6-148)
T 1 T 1
1 + ---- + --- δ s, i 1 + ---- + --- δ s, j
εi 4 εj 4

Otherwise,

S i, j = 1 (6-149)

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 =  ----------------------- (6-150)
 T c1 / 6   101325 2 / 3 

where ξ is calculated from the correlation of Jossi (Ref. 38), 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 (6-151)

– 0.40758 ρ r3 + 0.093324 ρ r4

ρ
ρ r = ----- (6-152)
ρc

1
ρ c = ------ (6-153)
Vc

The following mixture rules are used

366 | CHAPTER 6: THERMODYNAMICS

 RT c Z c
P c = ----------------- , V c =
Vc  x i V c, i , T c =  x i T c, i (6-154)
i
i

 x i Z c, i  xi Mi
Zc = ,M = (6-155)
t
i i

The values for critical volumes, Vc,i, critical temperatures, Tc,i, critical compressibility
factors, Zc,i and molecular weights, Mi must be specified for all species i.

The high pressure correction is available for the Wilke and Brokaw mixture models.
The vapor viscosity follows from

η v = η v, Wilke + Δη v, P (6-156)

where ηv,Wilke is calculated from Equation 6-143.

Pedersen Corresponding States Model

The corresponding states viscosity model of Pedersen (Ref. 39 - Ref. 40) applies to
both vapor and liquid phases of hydrocarbon mixtures. The selected reference species
is CH4.

The CH4 viscosity is calculated from Ref. 41, modified by Pedersen and Fredunsland
(Ref. 42) to avoid issues below 91 K where CH4 becomes solid

η CH = η CH 4, 0 + ρ CH 4 η CH , 1 + F 1 η CH , 2 + F 2 η CH , 3 (6-157)
4 4 4 4

where

H+1
F 1 = -------------- (6-158)
2

1–H
F 1 = -------------- (6-159)
2

exp ( ΔT ) – exp ( – ΔT )
H = ------------------------------------------------------------- (6-160)
exp ( ( ΔT ) + exp ( – ΔT ) )

ΔT = T – 91 (T ∈ K) (6-161)

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

THERMODYNAMIC MODELS AND THEORY | 367

 –L1 L2 L3
η CH4, 0 = ---------- + -----------
/
– ----------- (6-162)
T T 2 3 T1 / 3
+ L4 –L5 T 1 / 3 + L6 T 2 ⁄ 3 – L7 T + L8 T 4 ⁄ 3 – L9 T 5 / 3

The first density correction for the moderately dense gas is given by

T 2
η CH4, 1 = L 10 – L 11  1.4 – ln ---------- (6-163)
 168

The remainder is given by the empirical correlation

L 12   L 15 
η CH4, 2 = exp  --------- – L 13  exp  ( 10 ρ CH4 )  L 14 – ----------- + (6-164)
T    T 3 / 2
 ρ CH – ρ c, CH4 L 17 L 18  
4 - ( ρ CH )  L 16 + --------
 ------------------------------------ - + ---------  – 1
 ρ c, CH4  4  T T  2  

The correction term for solid CH4

L 19 L 22 
η CH4, 3 = exp  --------- – L 20  exp  ( 10 ρ CH 4 )  L 21 – -----------
T    T 3 / 2 (6-165)
ρ CH 4 – ρ c, CH 4 L L
+  ------------------------------------ ( ρ CH 4 )  L 23 + --------- + --------
25 
24
- – 1
 ρ c, CH   T T2   
4

with the values of the parameters L1 through L25 are listed in Table 6-5 below:
TABLE 6-5: METHANE VISCOSITY NUMERICAL COEFFICIENTS.

L1 2.090975·105 L10 1.696985927 L19 9.74602

L2 2.647269·105 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
L8 4.274152 L17 145.29023444
L9 0.08141531 L18 6127.6818706

Here, ρCH4 is used in g/cm3; the critical density is given by ρc,CH4 = 0.16284 g/cm3.
The following equation by McCarty (Ref. 43) is solved for the density of CH4

368 | CHAPTER 6: THERMODYNAMICS

  N 5 N 6
P = N 1 ρ CH T + ρ CH
2  – N 2 T + N 3 T – N 4 + ------- – ------2- (6-166)
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 6-6: COEFFICIENTS IN THE FUNCTIONAL FORM OF THE M cCARTY 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
N6 42738.409106 N18 0.57974531455·10-5 N30 0.4100678294·10-5
N7 0.76565285254·10-3 N19 0.0071648329297 N31 0.0014870043284
N8 0.48360724197 N20 0.12577853784·10-3 N32 3.151226153·10-9
N9 85.195473835 N21 0.0096 N33 0.2167077474·10-5
N10 16607.434721 N22 22240.102466 N34 0.2400055107·10-4
N11 0.37521074532·10-4 N23 1.4800512328·106
N12 0.028616309259 N24 50.498054887

With the viscosity and density of CH4 defined, the viscosity of any mixture, ηm, can be
calculated from the corresponding states principle

–1
Tc ------ Pc 2 / 3 Mm 1 / 2 α
η m =  ------------------ 6  -----------------  ---------------  ------------- η CH4, P 0, T 0 (6-167)
 T c, CH   P c, CH   M CH   α CH 
4 4 4 4

where CH4 viscosity ρCH4,P0,T0 is calculated at temperature, T0 and pressure P0

THERMODYNAMIC MODELS AND THEORY | 369

 T c, CH α CH
T 0 =  ------------------4 T  -------------4 (6-168)
 Tc   α 

P c, CH α CH
P 0 =  -----------------4 P  -------------4 (6-169)
Pc α

The following mixing rules are used for the critical properties, see Ref. 44:

  x i x j β i, j T c, i T c, j
(6-170)
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
(6-171)
i j
--------------------------------------------------------------
-
Pc =
 2

   xi xj βi, j
i j

T c, i 1 / 3  T c, j 1 / 3 3
β i, j =   ---------- + ---------- (6-172)
  P c, i  P c, j 

The parameter α is

–3 0.5173
α = 1 + 7.378 ×10 ρ r1.847 M m (6-173)

ρ
CH 4, P 0, T 0
ρ r = --------------------------
- (6-174)
ρ c, CH4

where

T c, CH
T 0 =  ------------------4 T (6-175)
 Tc 

P c, CH
P 0 =  -----------------4 P (6-176)
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 (6-177)

370 | CHAPTER 6: THERMODYNAMICS

where Equation 6-174 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 (6-178)

 xi Mi
2

i (6-179)
M W = --------------------
-
MN

 xi Mi
MN = (6-180)
i

where the power in Equation 6-178 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.

LIQUID THERMAL CONDUCTIVITY

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 = (6-181)
i

The pressure dependence is based on the work of Missenard (Ref. 45) where

λ l, m , P
----------------- = 1 + QP r0.7 (6-182)
λ l, m

where Q is correlated as

Q = -0.013693477 + 0.057427673T r + 0.001617831 ( T r ) ( ln P 1 ) (6-183)

and the following mixing rules are used

T
T r = ------ (6-184)
Tc

THERMODYNAMIC MODELS AND THEORY | 371

 P
P r = ------ (6-185)
Pc

RT c Z c
P c = ----------------- (6-186)
Vc

 x i V c, i
Vc = (6-187)
i

 x i T c, i
Tc = (6-188)
i

 x i Z c, i
Zc = (6-189)
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
(6-190)
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. 46 - Ref. 47). The pressure dependence is introduced using Equation 6-182 –
Equation 6-189. 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. 47) uses an ideal and excess
contribution

λ l, m = λ l, ideal + λ l, excess (6-191)

The ideal part is based on mass fractions

372 | CHAPTER 6: THERMODYNAMICS

 λ l, ideal =  ωi λi, l (6-192)
i

xi Mi
ω i = -------------------- (6-193)
xj Mj
j

The excess term is based on NRTL local concentrations

  ωi ωj Gj, i ( λj, i – λi, l )

i j
λ l, excess = ------------------------------------------------------------------
- (6-194)

ω j G j, i
j

where Gj,i follows from Equation 6-51. 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 = -------------------------------------------------------- (6-195)
ω i ω i, i + ω j ω j, j

which is symmetric, and on the diagonal,

λ i, i = λ i, l (6-196)

and

ω i, i = ω i ( ω i + ω j G j, i ) (6-197)

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 = -------------------------------------------------- (6-198)
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 6-182 – Equation 6-189. 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

THERMODYNAMIC MODELS AND THEORY | 373

 of zero on the diagonal and the matrix is symmetric. All off-diagonal values must be
specified. NRTL model is presented in Equation 6-49 to Equation 6-57.

Local Composition (Modified)

Rowley (Ref. 46) adapted the local composition model by replacing the mixing rule in
Equation 6-195 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 = ---------------------------------------------------------------------------------- (6-199)
M i ( ω i ω i, i ) + M j ( ω j ω j, j )

which he found to produce better model predictions in most cases where both the
Local Composition model and Power Law model have trouble. However, the model
is not as generally applicable; for instance, systems containing H2O are not well
described by this model due to the low molecular weight of H2O.

LIQUID VISCOSITY
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

 xi ln ηi, l
ln η l, m = (6-200)
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

 ωi ln ηi, l
ln η l, m = (6-201)
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.

374 | CHAPTER 6: THERMODYNAMICS

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 = (6-202)
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. 48), 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 (6-203)
σ vl = -------------------------------------------------------------
-
 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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THERMODYNAMIC MODELS AND THEORY | 379

380 | CHAPTER 6: THERMODYNAMICS
 7

Glossary

This Glossary of Terms contains application-specific terms used in the Chemical

Reaction Engineering 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.

381
 Glossary of Terms
absorption Uptake of a gas into the bulk of a liquid. Gas absorption takes place for
example in the liquid of a scrubber tower where an up-streaming gas is washed by a
down-going flow of a scrubber solution.

adsorption Attachment of a molecule or atom to a solid surface. Adsorption involves

a chemical bond between the adsorbed species and the surface.

anisotropy Variation of a transport property in different directions in a material. Is

often obtained from homogenization of regular structures, for example, monolithic
structures in tubular reactors.

Arrhenius rate equation Expression that relates the rate constant of a chemical
reaction to the exponential of the temperature.

batch reactor Reactor characterized by its operation, which means that the reactor
does reaches steady state.

bipolar plate Electrically conducting plate connected to the anode on one side and to
the cathode on the other side in an electrochemical cell.

Brinkman equations Extension of Darcy’s law in order to include the transport of

momentum through shear in porous media flow.

Butler-Volmer equation Expression that relates the reaction rate of an electron transfer
reaction on an electrode surface to the exponential of the overpotential. The equation
can be derived from the Arrhenius rate equation by accounting for the contribution of
the electric potential to the activation energy.

boundary layer Region in a fluid close to a solid surface. This region is characterized
by large gradients in velocity and is often treated with approximate methods because
it is difficult to geometrically resolve the large gradients found there.

chemisorption See adsorption.

continuous reactor Reactor that operates without interruption. This type of reactor is
characterized by its steady-state operation.

382 | CHAPTER 7: GLOSSARY

diffusion layer Fictitious layer in a fluid close to a solid surface where a chemical
reaction takes place. The flux of species perpendicular to the surface in this layer is
dominated by diffusion.

Darcy’s law Equation that gives the velocity vector as proportional to the pressure
gradient. Often used to describe flow in porous media.

electrokinetic flow Transport of fluid or charged particles within a fluid by means of

electric fields.

electroneutrality condition Condition that states that the sum of charges in a control
volume in an electrolyte should be zero.

electrophoresis Migration of charged electrolyte ions in an electric field.

electroosmosis Onset of a flow due to the application of an external electric field or

due to the formation of an electric field created by ion transport in membranes, for
example.

Euler flow Flow at high velocities, where incompressibility of the fluid is of importance
whereas the influence of viscous momentum transport is negligible.

Fick’s laws The first law relates the concentration gradients to the diffusive flux of a
solute infinitely diluted in a solvent. The second law introduces the first law into a
differential material balance for the solute.

fully developed laminar flow Laminar flow along a channel or pipe that only has
velocity components in the main direction of the flow. The velocity profile
perpendicular to the flow does not change downstream in the flow.

Hagen-Poiseuille equation See Poiseuille’s law.

heterogeneous reaction Reaction that takes place at the interface between two phases.

homogeneous reaction Reaction that takes place in the bulk of a solution.

law of the wall See wall function.

Maxwell-Stefan equations Set of equations that describe the diffusion of solutes and
solvent in a concentrated solution. In such a solution, the solutes interact with each
other and with the solvent.

GLOSSARY OF TERMS | 383

 migration The transport of charged species in an electrolyte due to the electric force
imposed by the electric field.

monolithic reactor Catalytic reactor made of one single piece of solid material.
Incorporates a catalytic structure in its often porous structure.

Navier-Stokes equations Equations for the momentum balances coupled to the

equation of continuity for a Newtonian incompressible fluid.

Nernst-Planck equation Equation that describes the flux of an ion through diffusion,
convection, and migration in an electric field. The equation is valid for diluted
electrolytes.

Newtonian flow Flow characterized by a constant viscosity or a viscosity that is

independent of the shear rate in the fluid.

physisorption See adsorption.

Poiseuille’s law Equation that relates the mass rate of flow in a tube as proportional to
the pressure difference per unit length and to the fourth power of the tube radius. The
law is valid for fully developed laminar flow.

Soret effect Mass diffusion in multicomponent mixtures due to temperature

gradients.

specific surface area Internal surface area of a porous structure given in area per unit
volume, which yields the unit one over unit length. Often used to characterize the
structure of porous catalysts.

streamline-diffusion stabilization A numerical technique for stabilization of the

numeric solution to a convection-dominated PDE by artificially adding diffusion in the
direction of the streamlines.

surface molar flux the tangential flux in the surface dimension as governed by
diffusion according to Fick’s law.

wall function Semi-empirical expression for the anisotropic flow close to a solid surface
used in turbulence models. Often based on negligible variations in pressure gradient
in the direction tangential to the surface.

384 | CHAPTER 7: GLOSSARY

I n d e x
A AC/DC Module 117 concentration (node)
activation energy 35 Nernst-Planck equations 256
adding species 117 transport of diluted species 192
additional sources (node) 79 concentration of species 117
adsorption 204, 218 concentration variables, scaling 63
Application Libraries window 21 continuity equation, Nernst-Planck equa-
application library examples tions 174
CHEMKIN 54 convection 132
convection and diffusion 188 convection, diffusion, and migration
migration in electric field 188 (node)
surface reactions 277 Nernst-Planck equations 253
transport of concentrated species 228 convective terms 31
transport of diluted species 183 convective terms, diluted species 124
variables with scope 29 convective terms, Nernst-Planck equa-
Arrhenius parameters 69, 99 tions 173
association factor of solvents 51 critical point 323

B batch reactor (constant volume) 44 CSTR (constant volume), defined 59

batch reactors, defined 59 CSTR (constant volume), theory 45

batch reactors, theory 43 CSV files 91

Batteries & Fuel Cells Module 117 current (node) 272

boundary electrolyte potential 272 current density (node) 258, 272

boundary nodes current discontinuity (node) 259

Nernst-Planck equations 252 D Darcy velocity 132

surface reactions 277 defining species concentration 117
transport of concentrated species 229 diffusion models 224
transport of diluted species 184, 268 diffusivity
Butler-Volmer equation 256 gas phase, solvents 50

C CFD Module 117 liquid phase, solvents 50

chemical equilibrium 27, 68, 98 dipole moment transport parameter 74,

chemical formula identification number 103

28 documentation 20

chemistry interface domain nodes

theory 34 electrophoretic transport interface

CHEMKIN 26, 53 268

common settings 19 Nernst-Planck equations 252

transport of concentrated species 229

INDEX| 385
 transport of diluted species 184 frequency factors 35
Dusty gas model 225 Freundlich exponent 138

E edge nodes G gas constant 35, 178

surface reactions 277 gas diffusion 151
electric insulation (node) 255 gas phase solvents 52
electrode-electrolyte interface coupling gas reacting fluids 60, 72, 96, 103
(node) Gibbs free energy 71, 101
transport of diluted species 201, 237
H half-cell 259
electrophoretic transport nterface 262
Heat Transfer Module 117
electrophoretictransport 262
Hygroscopic Swelling 213
emailing COMSOL 22
I importing
EnthalpyF 323
CHEMKIN files 53
EntropyF 323
inflow (node) 191, 274
Equilibrium Reaction
Nernst-Planck equations 257
theory for 122
transport of concentrated species 243
equilibrium reaction (node) 198, 246
initial values (node)
equilibrium reaction group (node) 77,
Nernst-Planck equations 255
106
reaction engineering 66
equilibrium reactions 41
surface reactions 279
experiment (node) 91
transport of concentrated species 241
F Faraday’s law 129
transport of diluted species 189
feed inlet (node) 81
insulation (node) 272
Fick equations and diffusivities 151
internet resources 19
Fick’s law approximation diffusion 157
irreversible reaction 27, 68, 98
Fick’s law diffusion model 226
J junction potentials 174
flash calculation
retrograde solution type 323 K kinetic gas theory 50
solution type 323–324 knowledge base, COMSOL 22
flash calculations 321 Knudsen diffusion 225
flux (node) 219, 274
L labeling rules, reaction nodes 29
Nernst-Planck equations 256
Langmuir constant 138
transport of concentrated species 242
Lennard-Jones potential 74, 103
transport of diluted species 192, 219,
line mass source (node)
274
species transport 195
flux discontinuity (node) 193
line source
Nernst-Planck equations 258
species transport 126
transport of concentrated species 245
liquid reacting fluids 60, 72, 96, 103
transport of diluted species 193

386 | I N D E X
M mass action law 34 pair nodes
mass action law, laminar flow 177 electrophoretic transport interface
mass based concentrations (node) 189 268
mass fraction (node) 242 surface reactions 277
mass fractions 117 transport of concentrated species 229
mass transport 150 transport of diluted species 184
Maxwell-Stefan diffusion model 225 parameter estimation, solver 110
Maxwell-Stefan diffusivity matrix 154 partially saturated porous media (node)
mixture-averaged diffusion model 155, 205
226 periodic condition (node)
monolayer adsorption 167 transport of diluted species 195
MPH-files 21 persistence
multicomponent diffusion 153 of thermodynamic packages 313
multiphase flash calculations 309 physics interfaces 15

N Nernst-Einstein relation 128, 187, 203, physics interfaces, common settings 19

207 plug flow reactors 48, 59

Nernst-Planck equations interface 249 point mass source (node)

theory 172 species transport 196

nernst-planck-poission equations inter- point nodes

face 261 surface reactions 277

no flux (node) 191 point source

Nernst-Planck equations 255 species transport 125

transport of concentrated species 244 porous electrode coupling (node) 200

nodes, common settings 19 porous media transport properties

nonconservative formulations 124, 174 (node) 202

potential (node) 272
O Ohm’s law 129
predefined expressions, reaction engi-
open boundary (node)
neering 54
Nernst-Planck equations 259
pseudo time step 175
transport of concentrated species 246
transport of diluted species 197 R reacting fluids, gases and liquids 60, 72,

outflow (node) 96, 103

electrophoretic transport 275 Reacting Volume 190, 222

Nernst-Planck equations 258 reaction (node) 67, 98

transport of concentrated species 244 reaction coefficients (node) 201

transport of diluted species 192 reaction engineering interface 58

theory 34
P packed bed reactors 140
reaction selection list 28
nonspherical particles 145
reaction terms 172

INDEX| 387
 reaction thermodynamics (node) 80, 108 space dimensions 15
Reactions species (node) 71, 102
in porous catalyst pellets 211 species activity (node) 80, 109
reactions (node) species group (node) 78, 108
Nernst-Planck equations 255 species names, syntax for 31
reacting flow, laminar flow 239 species source (node) 273
surface reactions 279 species thermodynamics (node) 80, 109
transport of concentrated species 240 species types 31
transport of diluted species 189 standard settings 19
reactive pellet bed 140 Stiel-Thodos equation 52
reactive pellet bed (node) 208 Stockmayer potential 74, 103
reactor types stoichiometric coefficients 71, 101
batch (constant volume) 44 stratified porous media 136
batch, defined 59 superficial volume averages, porous me-
batch, theory 43 dia 132
CSTR (constant volume), defined 59 Supporting Electrolytes 128
CSTR (constant volume), theory 45 supporting electrolytes
plug flow, definition 59 theory, Nernst-Planck equations 172
plug flow, theory 48 surface concentration (node) 280
semibatch, definition 59 surface equilibrium reaction (node) 199,
semibatch, theory 47 247
removing species 117 surface properties (node) 278
retardation factor 138 surface reactions interface 276
reversible reaction 27, 67, 98 theory 166
reversible reaction group (node) 75, 105 symmetry (node)
RF Module 117 Nernst-Planck equations 257
transport of concentrated species 245
S selecting
transport of diluted species 193
chemical species transport interfaces
113 T Tafel equation 256
space dimensions and physics interfac- technical support, COMSOL 22
es 15 temperature exponents 35
semibatch reactors 47, 59 theory
solute-solvent approximations 31 chemistry interface 34
solvents, association factor of 51 Nernst-Planck equations 172
solver settings, parameter estimation reaction engineering 34
110 surface reactions 166
solver time, discretization and 63 transport of concentrated species in-
Soret effect 158 terface 150

388 | I N D E X
 transport of diluted species in porous
media interface 121
transport of diluted species interface
120
thermal conductivity 52
thermal diffusion 158
thermodynamics package 308
adding 309
thickness
fracture 213
thin diffusion barrier (node) 197
Thin Impermeable Barrier 197
tortuosity factors 134
transport mechanisms 230, 234, 237
transport of concentrated species inter-
face 223
theory 150
transport of diluted species in porous
media interface 183
theory 121
transport of diluted species interface
179, 215
theory 120
turbulent mixing (node)
transport of concentrated species 238
transport of diluted species 188

U uniform scaling 63

V variable scope 29

W websites, COMSOL 22
Wilke-Chang equation 50

INDEX| 389
390 | I N D E X